U.S. patent application number 15/103318 was filed with the patent office on 2016-10-20 for surface treated copper foil, copper clad laminate, printed wiring board, electronic apparatus and method for manufacturing printed wiring board.
This patent application is currently assigned to JX Nippon Mining & Metals Corporation. The applicant listed for this patent is JX NIPPON MINING & METALS CORPORATION. Invention is credited to Hideta Arai, Kohsuke Arai, Atsushi Miki, Kaichiro Nakamuro.
Application Number | 20160303829 15/103318 |
Document ID | / |
Family ID | 53371240 |
Filed Date | 2016-10-20 |
United States Patent
Application |
20160303829 |
Kind Code |
A1 |
Arai; Hideta ; et
al. |
October 20, 2016 |
Surface Treated Copper Foil, Copper Clad Laminate, Printed Wiring
Board, Electronic Apparatus and Method for Manufacturing Printed
Wiring Board
Abstract
A surface treated copper foil which allows the resin to have
excellent transparency after removal of the copper foil by etching
is provided. The surface treated copper foil has one surface and
other surface each surface treated. An Sv defined by the following
expression (1) is 3.5 or more: Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
which is determined, after laminating one surface to each of both
surfaces of a polyimide resin substrate, removing the copper foil
on each of both surfaces by etching, and photographing a printed
matter with a linear mark, from the resulting observation spot
versus brightness graph; and the surface treated other surface of
the copper foil has a TD ten-spot average roughness Rz measured
with a laser microscope using laser light having a wavelength of
405 nm, of 0.35 .mu.m or more.
Inventors: |
Arai; Hideta; (Ibaraki,
JP) ; Miki; Atsushi; (Ibaraki, JP) ; Arai;
Kohsuke; (Ibaraki, JP) ; Nakamuro; Kaichiro;
(Ibaraki, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
JX NIPPON MINING & METALS CORPORATION |
Tokyo |
|
JP |
|
|
Assignee: |
JX Nippon Mining & Metals
Corporation
Tokyo
JP
|
Family ID: |
53371240 |
Appl. No.: |
15/103318 |
Filed: |
December 10, 2014 |
PCT Filed: |
December 10, 2014 |
PCT NO: |
PCT/JP2014/082765 |
371 Date: |
June 10, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B32B 2307/412 20130101;
H05K 2201/0108 20130101; H05K 2201/0154 20130101; H05K 1/09
20130101; H05K 2203/16 20130101; B32B 27/281 20130101; B32B 2457/00
20130101; H05K 3/30 20130101; B32B 15/08 20130101; H05K 1/0346
20130101; H05K 3/384 20130101; B32B 5/147 20130101; H05K 2203/0307
20130101; B32B 15/20 20130101; C25D 5/16 20130101; H05K 3/36
20130101; B32B 2457/08 20130101 |
International
Class: |
B32B 15/08 20060101
B32B015/08; B32B 15/20 20060101 B32B015/20; B32B 27/28 20060101
B32B027/28; H05K 3/38 20060101 H05K003/38; H05K 1/09 20060101
H05K001/09; H05K 1/03 20060101 H05K001/03; H05K 3/36 20060101
H05K003/36; H05K 3/30 20060101 H05K003/30; B32B 5/14 20060101
B32B005/14; C25D 5/16 20060101 C25D005/16 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 10, 2013 |
JP |
2013-255464 |
Claims
1. A surface treated copper foil having one surface and other
surface each surface treated, wherein an Sv defined by the
following expression (1) is 3.5 or more based on a brightness
curve: Sv=(.DELTA.B.times.0.1)/(t1-t2) (1) wherein the brightness
curve is obtained, after laminating one surface of the copper foil
to each of both surfaces of a polyimide resin substrate, removing
the copper foil on each of both surfaces by etching, placing a
printed matter with a linear mark under the exposed polyimide resin
substrate, and photographing the printed matter through the
polyimide resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the printed matter for the
respective observation spots along the direction perpendicular to
the extending direction of the observed linear mark, the difference
between the top average Bt and the bottom average Bb in the
brightness curve extending from an end of the mark to a portion
without the mark is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the linear mark among the intersections of
the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the linear mark among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and wherein the surface treated
other surface of the copper foil has a TD ten-spot average
roughness Rz measured with a laser microscope using laser light
having a wavelength of 405 nm, of 0.35 .mu.m or more.
2. The surface treated copper foil according to claim 1, wherein
the surface treated other surface of the copper foil has a TD
arithmetic average roughness Ra measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.05 .mu.m or
more.
3. A surface treated copper foil having one surface and other
surface each surface treated, wherein an Sv defined by the
following expression (1) is 3.5 or more based on a brightness
curve: Sv=(.DELTA.B.times.0.1)/(t1-t2) (1) wherein the brightness
curve is obtained, after laminating one surface of the copper foil
to each of both surfaces of a polyimide resin substrate, removing
the copper foil on each of both surfaces by etching, placing a
printed matter with a linear mark under the exposed polyimide resin
substrate, and photographing the printed matter through the
polyimide resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the printed matter for the
respective observation spots along the direction perpendicular to
the extending direction of the observed linear mark, the difference
between the top average Bt and the bottom average Bb in the
brightness curve extending from an end of the mark to a portion
without the mark is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the linear mark among the intersections of
the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the linear mark among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and wherein the surface treated
other surface of the copper foil has a TD arithmetic average
roughness Ra measured with a laser microscope using laser light
having a wavelength of 405 nm, of 0.05 .mu.m or more.
4. The surface treated copper foil according to claim 1, wherein
the surface treated other surface of the copper foil has a TD root
mean square height Rq measured with a laser microscope using laser
light having a wavelength of 405 nm, of 0.08 .mu.m or more.
5. A surface treated copper foil having one surface and other
surface each surface treated, wherein an Sv defined by the
following expression (1) is 3.5 or more based on a brightness
curve: Sv=(.DELTA.B.times.0.1)/(t1-t2) (1) wherein the brightness
curve is obtained, after laminating one surface of the copper foil
to each of both surfaces of a polyimide resin substrate, removing
the copper foil on each of both surfaces by etching, placing a
printed matter with a linear mark under the exposed polyimide resin
substrate, and photographing the printed matter through the
polyimide resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the printed matter for the
respective observation spots along the direction perpendicular to
the extending direction of the observed linear mark, the difference
between the top average Bt and the bottom average Bb in the
brightness curve extending from an end of the mark to a portion
without the mark is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the linear mark among the intersections of
the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the linear mark among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and wherein the surface treated
other surface of the copper foil has a TD root mean square height
Rq measured with a laser microscope using laser light having a
wavelength of 405 nm, of 0.08 .mu.m or more.
6. The surface treated copper foil according to claim 1, wherein
the surface treatment of the other surface is a roughening
treatment.
7. The surface treated copper foil according to claim 1, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
8. The surface treated copper foil according to claim 7, wherein
.DELTA.B in the observation spot versus brightness graph produced
from the photographed image is 50 or more.
9. The surface treated copper foil according to claim 1, wherein
the Sv defined by the expression (1) in the brightness curve is 3.9
or more.
10. The surface treated copper foil according to claim 9, wherein
the Sv defined by the expression (1) in the brightness curve is 5.0
or more.
11. The surface treated copper foil according to claim 1, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
12. The surface treated copper foil according to claim 11, wherein
the MD glossiness at 60 degrees is 90 to 250%.
13. The surface treated copper foil according to claim 11, wherein
the one surface has a TD ten-spot average roughness Rz measured
with a contact roughness measuring tester, of 0.30 to 0.60
.mu.m.
14. The surface treated copper foil according to claim 11, wherein
the A/B is 2.00 to 2.20.
15. The surface treated copper foil according to claim 11, wherein
the roughening treated surface has a ratio F of the MD glossiness
at 60 degrees to the TD glossiness at 60 degrees (F=(MD glossiness
at 60 degrees)/(TD glossiness at 60 degrees)) of 0.80 to 1.40.
16. The surface treated copper foil according to claim 15, wherein
the roughening treated surface has a ratio F of the MD glossiness
at 60 degrees to the TD glossiness at 60 degrees (F=(MD glossiness
at 60 degrees)/(TD glossiness at 60 degrees)) of 0.90 to 1.35.
17. The surface treated copper foil according to claim 1, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
18. The surface treated copper foil according to claim 17, wherein
the one surface has a root mean square height Rq of 0.25 to 0.60
.mu.m.
19. The surface treated copper foil according to claim 1, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
20. The surface treated copper foil according to claim 19, wherein
the one surface has a skewness Rsk of -0.30 to 0.39.
21. The surface treated copper foil according to claim 1, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
22. The surface treated copper foil according to claim 21, wherein
the ratio E/G is 2.95 to 21.42.
23. The surface treated copper foil according to claim 1, wherein
the one surface has a TD ten-spot average roughness Rz measured
with a contact roughness measuring tester, of 0.20 to 0.64
.mu.m.
24. The surface treated copper foil according to claim 23, wherein
the one surface has a TD ten-spot average roughness Rz measured
with a contact roughness measuring tester, of 0.40 to 0.62
.mu.m.
25. The surface treated copper foil according to claim 1, wherein
the D/C of the three-dimensional surface area D to the
two-dimensional surface area (the surface area of the surface shown
in plan view) C of the one surface is 1.0 to 1.7.
26. The surface treated copper foil according to claim 25, wherein
the D/C is 1.0 to 1.6.
27. A copper clad laminate comprising a lamination of the surface
treated copper foil according to claim 1 and a resin substrate.
28. A printed wiring board comprising the surface treated copper
foil according to claim 1.
29. An electronic apparatus comprising the printed wiring board
according to claim 28.
30. A method for manufacturing a printed wiring board having two or
more connected printed wiring boards comprising connecting two or
more of the printed wiring boards according to claim 28.
31. A method for manufacturing a printed wiring board having two or
more connected printed wiring boards comprising at least the step
of connecting at least one printed wiring board according to claim
28 to another printed wiring board according to claim 28 or to a
printed wiring board other than the printed wiring board according
to claim 28.
32. (canceled)
33. A method for manufacturing a printed wiring board, comprising
the step of connecting the printed wiring board according to claim
28 to a component.
34. A method for manufacturing a printed wiring board having two or
more connected printed wiring boards, comprising at least the step
of connecting at least one printed wiring board according to claim
28 to another printed wiring board according to claim 28 or a
printed wiring board other than the printed wiring board according
to claim 28, and the step of connecting a printed wiring board
having two or more of the connected printed wiring boards according
to claim 28 or the printed wiring boards manufactured by a method
for manufacturing a printed wiring board having two or more
connected printed wiring boards comprising at least the step of
connecting at least one printed wiring board according to claim 28
to another printed wiring board according to claim 28 or to a
printed wiring board other than the printed wiring board according
to claim 28, to a component.
35.-48. (canceled)
49. The surface treated copper foil according to claim 2, wherein
the surface treated other surface of the copper foil has a TD root
mean square height Rq measured with a laser microscope using laser
light having a wavelength of 405 nm, of 0.08 .mu.m or more.
50. The surface treated copper foil according to claim 3, wherein
the surface treated other surface of the copper foil has a TD root
mean square height Rq measured with a laser microscope using laser
light having a wavelength of 405 nm, of 0.08 .mu.m or more.
51. The surface treated copper foil according to claim 1,
satisfying one, two, or three items of the following items (1) to
(3); (1) the surface treated other surface of the copper foil has a
TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.40 .mu.m or
more, (2) the surface treated other surface of the copper foil has
a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.08
.mu.m or more, (3) the surface treated other surface of the copper
foil has a TD root mean square height Rq measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.10
.mu.m or more.
52. The surface treated copper foil according to claim 3,
satisfying one, two, or three items of the following items (1) to
(3); (1) the surface treated other surface of the copper foil has a
TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.40 .mu.m or
more, (2) the surface treated other surface of the copper foil has
a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.08
.mu.m or more, (3) the surface treated other surface of the copper
foil has a TD root mean square height Rq measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.10
.mu.m or more.
53. The surface treated copper foil according to claim 5,
satisfying one, two, or three items of the following items (1) to
(3); (1) the surface treated other surface of the copper foil has a
TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.40 .mu.m or
more, (2) the surface treated other surface of the copper foil has
a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.08
.mu.m or more, (3) the surface treated other surface of the copper
foil has a TD root mean square height Rq measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.10
.mu.m or more.
54. The surface treated copper foil according to claim 2, wherein
the surface treatment of the other surface is a roughening
treatment.
55. The surface treated copper foil according to claim 3, wherein
the surface treatment of the other surface is a roughening
treatment.
56. The surface treated copper foil according to claim 4, wherein
the surface treatment of the other surface is a roughening
treatment.
57. The surface treated copper foil according to claim 49, wherein
the surface treatment of the other surface is a roughening
treatment.
58. The surface treated copper foil according to claim 50, wherein
the surface treatment of the other surface is a roughening
treatment.
59. The surface treated copper foil according to claim 5, wherein
the surface treatment of the other surface is a roughening
treatment.
60. The surface treated copper foil according to claim 2, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
61. The surface treated copper foil according to claim 3, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
62. The surface treated copper foil according to claim 4, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
63. The surface treated copper foil according to claim 49, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
64. The surface treated copper foil according to claim 50, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
65. The surface treated copper foil according to claim 5, wherein
the difference .DELTA.B (.DELTA.B=Bt-Bb) between the top average Bt
and the bottom average Bb in the brightness curve extending from
the end of the mark to the portion without the mark is 40 or
more.
66. The surface treated copper foil according to claim 2, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
67. The surface treated copper foil according to claim 3, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
68. The surface treated copper foil according to claim 4, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
69. The surface treated copper foil according to claim 49, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
70. The surface treated copper foil according to claim 50, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
71. The surface treated copper foil according to claim 5, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
72. The surface treated copper foil according to claim 7, wherein
the surface treatment of the one surface is a roughening treatment,
the roughening treated surface has a TD ten-spot average roughness
Rz measured with a contact roughness measuring tester, of 0.20 to
0.80 .mu.m, the roughening treated surface has an MD glossiness at
60 degrees of 76 to 350%, and the ratio A/B of the surface area A
of the roughening treated surface to the area B of the roughening
treated surface shown in the plan view from one surface side of the
copper foil is 1.90 to 2.40.
73. The surface treated copper foil according to claim 2, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
74. The surface treated copper foil according to claim 3, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
75. The surface treated copper foil according to claim 4, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
76. The surface treated copper foil according to claim 49, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
77. The surface treated copper foil according to claim 50, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
78. The surface treated copper foil according to claim 5, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
79. The surface treated copper foil according to claim 72, wherein
the one surface has a root mean square height Rq of 0.14 to 0.63
.mu.m.
80. The surface treated copper foil according to claim 2, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
81. The surface treated copper foil according to claim 3, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
82. The surface treated copper foil according to claim 4, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
83. The surface treated copper foil according to claim 49, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
84. The surface treated copper foil according to claim 50, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
85. The surface treated copper foil according to claim 5, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
86. The surface treated copper foil according to claim 79, wherein
the one surface has a skewness Rsk of -0.35 to 0.53 based on JIS B
0601-2001.
87. The surface treated copper foil according to claim 2, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
88. The surface treated copper foil according to claim 3, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
89. The surface treated copper foil according to claim 4, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
90. The surface treated copper foil according to claim 49, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
91. The surface treated copper foil according to claim 50, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
92. The surface treated copper foil according to claim 5, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
93. The surface treated copper foil according to claim 86, wherein
the ratio E/G of the volume E of the projection portion of the one
surface to the surface area G of the one surface shown in plan view
is 2.11 to 23.91.
94. The surface treated copper foil according to claim 3, wherein
the one surface has a TD ten-spot average roughness Rz measured
with a contact roughness measuring tester, of 0.20 to 0.64
.mu.m.
95. The surface treated copper foil according to claim 5, wherein
the one surface has a TD ten-spot average roughness Rz measured
with a contact roughness measuring tester, of 0.20 to 0.64
.mu.m.
96. The surface treated copper foil according to claim 3, wherein
the D/C of the three-dimensional surface area D to the
two-dimensional surface area (the surface area of the surface shown
in plan view) C of the one surface is 1.0 to 1.7.
97. The surface treated copper foil according to claim 5, wherein
the D/C of the three-dimensional surface area D to the
two-dimensional surface area (the surface area of the surface shown
in plan view) C of the one surface is 1.0 to 1.7.
98. A copper clad laminate comprising a lamination of the surface
treated copper foil according to claim 3 and a resin substrate.
99. A copper clad laminate comprising a lamination of the surface
treated copper foil according to claim 5 and a resin substrate.
100. A printed wiring board comprising the surface treated copper
foil according to claim 3.
101. A printed wiring board comprising the surface treated copper
foil according to claim 5.
Description
TECHNICAL FIELD
[0001] The present invention relates to a surface treated copper
foil, a copper clad laminate, a printed wiring board, an electronic
apparatus and a method for manufacturing a printed wiring board,
and more specifically, a surface treated copper foil, a copper clad
laminate, a printed wiring board, an electronic apparatus and a
method for manufacturing a printed wiring board, suitable for
applications where transparency of a resin which remains after
etching a copper foil is required.
BACKGROUND ART
[0002] A flexible printed wiring board (hereinafter referred to as
FPC) is employed in a compact electronic apparatus such as a smart
phone and a tablet PC due to the easiness of wiring and the
lightness. Due to the recent improvement of functionality of
electronic apparatuses, the signal transmission rate has been
accelerated, so that impedance matching is an important factor even
for an FPC. In order to achieve impedance matching for the
increased signal capacity, a resin insulating layer (e.g.,
polyimide) as the base of an FPC has been thickened. In order to
meet the demand for densification of wirings, multilayering of an
FPC has been further developed. On the other hand, when an FPC is
processed for bonding to a liquid crystal substrate and mounting an
IC chip, alignment is performed with a positioning pattern which is
visually recognized through a resin insulating layer remained after
etching of the copper foil of a laminate composed of the copper
foil and the resin insulating layer. The visibility of the resin
insulating layer is therefore important.
[0003] A copper clad laminate composed of a laminate of a copper
foil and a resin insulating layer may be manufactured from a rolled
copper foil having a roughened plated surface. The rolled copper
foil is usually manufactured from tough pitch copper (oxygen
content: 100 to 500 ppm by weight) or oxygen-free copper (oxygen
content: 10 ppm by weight or less) as a raw material ingot, which
is hot rolled and then subjected to repeated cold rolling and
annealing to a predetermined thickness.
[0004] Examples of the techniques include the followings. Patent
Literature 1 discloses an invention of a copper clad laminate of a
polyimide film and a low profile copper foil, which allows a film
after etching of the copper foil to have a light transmittance of
40% or more at a wavelength of 600 nm, with a haze value (HAZE) of
30% or less and an adhesive strength of 500 N/m or more.
[0005] Patent Literature 2 discloses an invention of a chip on
flexible (COF) flexible printed wiring board having an insulating
layer on which a conductive layer of electrolytic copper foil is
laminated, allowing the insulating layer in an etched region after
circuit formation by etching of the conductive layer to have a
light transmittance of 50% or more. The electrolytic copper foil
includes a rustproof layer of nickel-zinc alloy at the joint area
bonded to the insulating layer. The joint area has a surface
roughness (Rz) of 0.05 to 1.5 .mu.m and a specular gloss of 250 or
more at an incident angle of 60.degree..
[0006] Patent Literature 3 discloses an invention of a method for
processing a copper foil for a printed circuit, including forming a
cobalt-nickel alloy plated layer after surface roughening treatment
of the copper foil surface by plating with a copper-cobalt-nickel
alloy, and further forming a zinc-nickel alloy plated layer.
CITATION LIST
Patent Literature
[Patent Literature 1]
[0007] Japanese Patent Laid-Open No. 2004-98659
[Patent Literature 2]
[0008] International Publication No. WO 2003/096776
[Patent Literature 3]
[0009] Japanese Patent No. 2849059
SUMMARY OF INVENTION
Technical Problem
[0010] In Patent Literature 1, the adhesiveness of a low profile
copper foil is improved by blackening treatment or with an organic
treating agent after plating treatment. The copper foil causes
disconnection due to fatigue in some cases for use in need of
flexibility of a copper clad laminate, and has poor transparency of
a resin in some cases.
[0011] In Patent Literature 2, since no roughening treatment is
performed, the adhesion strength between a copper foil and a resin
is low and insufficient for use other than as a COF flexible
printed wiring board.
[0012] Furthermore, although a treatment method according to Patent
Literature 3 allows for fining of a copper foil with Cu--Co--Ni, a
resin bonded to the copper foil has insufficient transparency after
removal of the copper foil by etching.
[0013] The present invention provides a surface treated copper foil
which allows the resin to have excellent transparency after removal
of the copper foil by etching.
Solution to Problem
[0014] As a result of earnest research effort, the present
inventors found that the transparency of a resin after removal of a
copper foil by etching is affected without influence of the type
and the thickness of a substrate resin film by the following. A
surface treated copper foil is subjected to a predetermined surface
treatment. The surface treated surface of the copper foil is
laminated and removed so as to form a polyimide substrate, under
which a marked printed matter is placed. The printed matter is
photographed through the polyimide substrate with a CCD camera. A
graph of observation spot versus brightness is produced from the
image of the marked part. An attention is paid to the gradient of
the brightness curve drawn in the graph in the vicinity of the end
of the mark such that the gradient of the brightness curve is
controlled.
[0015] An aspect of the present invention accomplished based on the
finding is a surface treated copper foil having one surface and
other surface each surface treated, wherein an Sv defined by the
following expression (1) is 3.5 or more based on a brightness
curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0016] wherein the brightness curve is obtained, after laminating
one surface of the copper foil to each of both surfaces of a
polyimide resin substrate, removing the copper foil on each of both
surfaces by etching, placing a printed matter with a linear mark
under the exposed polyimide resin substrate, and photographing the
printed matter through the polyimide resin substrate with a CCD
camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the printed matter for the respective observation spots along the
direction perpendicular to the extending direction of the observed
linear mark, and the difference between the top average Bt and the
bottom average Bb in the brightness curve extending from an end of
the mark to a portion without the mark is represented by .DELTA.B
(.DELTA.B=Bt-Bb), and wherein t1 represents a value pointing the
position of the intersection closest to the linear mark among the
intersections of the brightness curve and Bt in the observation
spot versus brightness graph, and t2 represents a value pointing
the position of the intersection closest to the linear mark among
the intersections of the brightness curve and 0.1.DELTA.B in the
range from the intersections of the brightness curve and Bt to a
depth of 0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.35 .mu.m or
more.
[0017] One embodiment of the surface treated copper foil of the
present invention, the surface treated other surface of the copper
foil has a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.05
.mu.m or more.
[0018] Another aspect of the present invention is a surface treated
copper foil having one surface and other surface each surface
treated,
wherein an Sv defined by the following expression (1) is 3.5 or
more based on a brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0019] wherein the brightness curve is obtained, after laminating
one surface of the copper foil to each of both surfaces of a
polyimide resin substrate, removing the copper foil on each of both
surfaces by etching, placing a printed matter with a linear mark
under the exposed polyimide resin substrate, and photographing the
printed matter through the polyimide resin substrate with a CCD
camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the printed matter for the respective observation spots along the
direction perpendicular to the extending direction of the observed
linear mark, and the difference between the top average Bt and the
bottom average Bb in the brightness curve extending from an end of
the mark to a portion without the mark is represented by .DELTA.B
(.DELTA.B=Bt-Bb), and wherein t1 represents a value pointing the
position of the intersection closest to the linear mark among the
intersections of the brightness curve and Bt in the observation
spot versus brightness graph, and t2 represents a value pointing
the position of the intersection closest to the linear mark among
the intersections of the brightness curve and 0.1.DELTA.B in the
range from the intersections of the brightness curve and Bt to a
depth of 0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD arithmetic average roughness Ra measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.05 .mu.m or
more.
[0020] In another embodiment of the surface treated copper foil of
the present invention, the surface treated other surface of the
copper foil has a TD root mean square height Rq measured with a
laser microscope using laser light having a wavelength of 405 nm,
of 0.08 .mu.m or more.
[0021] Further another aspect of the present invention is a surface
treated copper foil having one surface and other surface each
surface treated,
wherein an Sv defined by the following expression (1) is 3.5 or
more based on a brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0022] wherein the brightness curve is obtained, after laminating
one surface of the copper foil to each of both surfaces of a
polyimide resin substrate, removing the copper foil on each of both
surfaces by etching, placing a printed matter with a linear mark
under the exposed polyimide resin substrate, and photographing the
printed matter through the polyimide resin substrate with a CCD
camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the printed matter for the respective observation spots along the
direction perpendicular to the extending direction of the observed
linear mark, and the difference between the top average Bt and the
bottom average Bb in the brightness curve extending from an end of
the mark to a portion without the mark is represented by .DELTA.B
(.DELTA.B=Bt-Bb), and wherein t1 represents a value pointing the
position of the intersection closest to the linear mark among the
intersections of the brightness curve and Bt in the observation
spot versus brightness graph, and t2 represents a value pointing
the position of the intersection closest to the linear mark among
the intersections of the brightness curve and 0.1.DELTA.B in the
range from the intersections of the brightness curve and Bt to a
depth of 0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD root mean square height Rq measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.08 .mu.m or
more.
[0023] In further another embodiment of the surface treated copper
foil of the present invention, the surface treatment of the other
surface is a roughening treatment.
[0024] In further another embodiment of the surface treated copper
foil of the present invention, the difference between the top
average Bt and the bottom average Bb in the brightness curve
extending from the end of the mark to the portion without the mark
.DELTA.B (.DELTA.B=Bt-Bb) is 40 or more.
[0025] In another embodiment of the surface treated copper foil of
the present invention, .DELTA.B in the observation spot versus
brightness graph produced from the photographed image is 50 or
more.
[0026] In further another embodiment of the surface treated copper
foil of the present invention, the Sv defined by the expression (1)
in the brightness curve is 3.9 or more.
[0027] In further another embodiment of the surface treated copper
foil of the present invention, the Sv defined by the expression (1)
in the brightness curve is 5.0 or more.
[0028] In further another embodiment of the surface treated copper
foil of the present invention, the surface treatment of the one
surface is a roughening treatment, the roughening treated surface
has a TD ten-spot average roughness Rz measured with a contact
roughness measuring tester, of 0.20 to 0.80 .mu.m, the roughening
treated surface has an MD glossiness at 60 degrees of 76 to 350%,
and the ratio A/B of the surface area A of the roughened grains to
the area B of the roughened grains shown in the plan view from one
surface side of the copper foil is 1.90 to 2.40.
[0029] In further another embodiment of the surface treated copper
foil of the present invention, the MD glossiness at 60 degrees is
90 to 250%.
[0030] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a TD ten-spot
average roughness Rz measured with a contact roughness measuring
tester, of 0.30 to 0.60 .mu.m.
[0031] In further another embodiment of the surface treated copper
foil of the present invention, the A/B is 2.00 to 2.20.
[0032] In further another embodiment of the surface treated copper
foil of the present invention, the roughening treated surface has a
ratio F of the MD glossiness at 60 degrees to the TD glossiness at
60 degrees (F=(MD glossiness at 60 degrees)/(TD glossiness at 60
degrees)) of 0.80 to 1.40.
[0033] In further another embodiment of the surface treated copper
foil of the present invention, the roughening treated surface has a
ratio F of the MD glossiness at 60 degrees to the TD glossiness at
60 degrees (F=(MD glossiness at 60 degrees)/(TD glossiness at 60
degrees)) of 0.90 to 1.35.
[0034] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a root mean
square height Rq of 0.14 to 0.63 .mu.m.
[0035] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a root mean
square height Rq of 0.25 to 0.60 .mu.m.
[0036] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a skewness Rsk
of -0.35 to 0.53 based on JIS B 0601-2001.
[0037] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a skewness Rsk
of -0.30 to 0.39.
[0038] In further another embodiment of the surface treated copper
foil of the present invention, the ratio E/G of the volume E of the
projection portion of the surface treated surface to the surface
area G of the one surface shown in plan view is 2.11 to 23.91.
[0039] In further another embodiment of the surface treated copper
foil of the present invention, the ratio E/G is 2.95 to 21.42.
[0040] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a TD ten-spot
average roughness Rz measured with a contact roughness measuring
tester, of 0.20 to 0.64 .mu.m.
[0041] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a TD ten-spot
average roughness Rz measured with a contact roughness measuring
tester, of 0.40 to 0.62 .mu.m.
[0042] In further another embodiment of the surface treated copper
foil of the present invention, the one surface has a ratio D/C of
the three-dimensional surface area D to the two-dimensional surface
area (the surface area of the surface in plan view) C of 1.0 to
1.7.
[0043] In further another embodiment of the surface treated copper
foil of the present invention, the D/C is 1.0 to 1.6.
[0044] Further another aspect of the present invention is a copper
clad laminate comprising a lamination of the surface treated copper
foil of the present invention and a resin substrate.
[0045] Further another aspect of the present invention is a printed
wiring board comprising the surface treated copper foil of the
present invention.
[0046] Further another aspect of the present invention is an
electronic apparatus comprising the printed wiring board of the
present invention.
[0047] Further another aspect of the present invention is a method
for manufacturing a printed wiring board having two or more
connected printed wiring boards comprising connecting two or more
of the printed wiring boards of the present invention.
[0048] Further another aspect of the present invention is a method
for manufacturing a printed wiring board having two or more
connected printed wiring boards comprising the step of connecting
at least one printed wiring board of the present invention to
another printed wiring board of the present invention or to a
printed wiring board other than the printed wiring board of the
present invention.
[0049] Further another aspect of the present invention is an
electronic apparatus comprising at least one printed wiring board
connected to at least one printed wiring board of the present
invention.
[0050] Further another aspect of the present invention is a method
for manufacturing a printed wiring board, comprising at least the
step of connecting the printed wiring board of the present
invention to a component.
[0051] Further another aspect of the present invention is a method
for manufacturing a printed wiring board having two or more
connected printed wiring boards, comprising at least the step of
connecting at least one printed wiring board of the present
invention to another printed wiring board of the present invention
or to a printed wiring board other than the printed wiring board of
the present invention, and the step of connecting the printed
wiring board of the present invention or a printed wiring board
having two or more of the connected printed wiring boards of the
present invention to a component.
[0052] Further another aspect of the present invention is a printed
wiring board having an insulating resin substrate and a copper
circuit arranged on the insulating resin substrate,
wherein the copper circuit has one surface facing the insulating
resin substrate and other surface treated surface; wherein an Sv
defined by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0053] wherein the brightness curve is obtained, in photographing
the copper circuit through the insulating resin substrate with a
CCD camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the copper circuit for the respective observation spots along the
direction perpendicular to the extending direction of the observed
copper circuit, the top average and the bottom average in the
brightness curve extending from an end of the copper circuit to a
portion without the copper circuit are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the copper circuit among the intersections
of the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the copper circuit among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper circuit has
a TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.35 .mu.m or
more.
[0054] In another embodiment of the printed wiring board of the
present invention, the surface treated other surface of the copper
foil has a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.05
.mu.m or more.
[0055] Further another aspect of the present invention is a printed
wiring board having an insulating resin substrate and a copper
circuit arranged on the insulating resin substrate,
wherein the copper circuit has one surface facing the insulating
resin substrate and other surface treated surface; wherein an Sv
defined by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0056] wherein the brightness curve is obtained, in photographing
the copper circuit through the insulating resin substrate with a
CCD camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the copper circuit for the respective observation spots along the
direction perpendicular to the extending direction of the observed
copper circuit, the top average and the bottom average in the
brightness curve extending from an end of the copper circuit to a
portion without the copper circuit are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the copper circuit among the intersections
of the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the copper circuit among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper circuit has
a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.05
.mu.m or more.
[0057] In further another embodiment of the printed wiring board of
the present invention, the surface treated other surface of the
copper foil has a TD root mean square height Rq measured with a
laser microscope using laser light having a wavelength of 405 nm,
of 0.08 .mu.m or more.
[0058] Further another aspect of the present invention is a printed
wiring board having an insulating resin substrate and a copper
circuit arranged on the insulating resin substrate,
wherein the copper circuit has one surface facing the insulating
resin substrate and other surface treated surface; wherein an Sv
defined by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0059] wherein the brightness curve is obtained, in photographing
the copper circuit through the insulating resin substrate with a
CCD camera, from an observation spot versus brightness graph of
measurement results of the brightness of the photographed image of
the copper circuit for the respective observation spots along the
direction perpendicular to the extending direction of the observed
copper circuit, the top average and the bottom average in the
brightness curve extending from an end of the copper circuit to a
portion without the copper circuit are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the copper circuit among the intersections
of the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents a value pointing the position
of the intersection closest to the copper circuit among the
intersections of the brightness curve and 0.1.DELTA.B in the range
from the intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper circuit has
a TD root mean square height Rq measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.08 .mu.m or
more.
[0060] In further another embodiment of the printed wiring board of
the present invention, the surface treatment of the other surface
is a roughening treatment.
[0061] Further another aspect of the present invention is a copper
clad laminate having an insulating resin substrate and a copper
foil arranged on the insulating resin substrate,
wherein the copper foil has one surface facing the insulating resin
substrate and other surface treated surface; wherein an Sv defined
by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0062] wherein the brightness curve is obtained, after etching the
copper foil of the copper clad laminate to provide a linear copper
foil, and photographing the linear copper foil through the
insulating resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the linear copper foil for
the respective observation spots along the direction perpendicular
to the extending direction of the observed linear copper foil, the
top average and the bottom average in the brightness curve
extending from an end of the linear copper foil to a portion
without the linear copper foil are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the surface treated linear copper foil
among the intersections of the brightness curve and Bt in the
observation spot versus brightness graph, and t2 represents a value
pointing the position of the intersection closest to the surface
treated linear copper foil among the intersections of the
brightness curve and 0.1.DELTA.B in the range from the
intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.35 .mu.m or
more.
[0063] In one embodiment of the copper clad laminate of the present
invention, the surface treated other surface of the copper foil has
a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.05
.mu.m or more.
[0064] Further another aspect of the present invention is a copper
clad laminate having an insulating resin substrate and a copper
foil arranged on the insulating resin substrate,
wherein the copper foil has one surface facing the insulating resin
substrate and other surface treated surface; wherein an Sv defined
by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0065] wherein the brightness curve is obtained, after etching the
copper foil of the copper clad laminate to provide a linear copper
foil, and photographing the linear copper foil through the
insulating resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the linear copper foil for
the respective observation spots along the direction perpendicular
to the extending direction of the observed linear copper foil, the
top average and the bottom average in the brightness curve
extending from an end of the linear copper foil to a portion
without the linear copper foil are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the surface treated linear copper foil
among the intersections of the brightness curve and Bt in the
observation spot versus brightness graph, and t2 represents a value
pointing the position of the intersection closest to the surface
treated linear copper foil among the intersections of the
brightness curve and 0.1.DELTA.B in the range from the
intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD arithmetic average roughness Ra measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.05 .mu.m or
more.
[0066] In another embodiment of the copper clad laminate of the
present invention, the surface treated other surface of the copper
foil has a TD root mean square height Rq measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.08
.mu.m or more.
[0067] Further another aspect of the present invention is a copper
clad laminate having an insulating resin substrate and a copper
foil arranged on the insulating resin substrate,
wherein the copper foil has one surface facing the insulating resin
substrate and other surface treated surface; wherein an Sv defined
by the following expression (1) is 3.5 or more based on a
brightness curve:
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0068] wherein the brightness curve is obtained, after etching the
copper foil of the copper clad laminate to provide a linear copper
foil, and photographing the linear copper foil through the
insulating resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the linear copper foil for
the respective observation spots along the direction perpendicular
to the extending direction of the observed linear copper foil, the
top average and the bottom average in the brightness curve
extending from an end of the linear copper foil to a portion
without the linear copper foil are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the surface treated linear copper foil
among the intersections of the brightness curve and Bt in the
observation spot versus brightness graph, and t2 represents a value
pointing the position of the intersection closest to the surface
treated linear copper foil among the intersections of the
brightness curve and 0.1.DELTA.B in the range from the
intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference; and
wherein the surface treated other surface of the copper foil has a
TD root mean square height Rq measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.08 .mu.m or
more.
[0069] In further another embodiment of the copper clad laminate of
the present invention, the surface treatment of the other surface
is a roughening treatment.
[0070] Further another aspect of the present invention is a printed
wiring board manufactured with the copper clad laminate of the
present invention.
Advantageous Effects of Invention
[0071] The present invention can provide a surface treated copper
foil which allows the resin to have excellent transparency after
removal of the copper foil by etching.
BRIEF DESCRIPTION OF DRAWINGS
[0072] FIG. 1 is a schematic diagram for defining Bt and Bb.
[0073] FIG. 2 is a schematic diagram for defining t1, t2, and
Sv.
[0074] FIG. 3 is a schematic diagram illustrating the constitution
of a photographic device and a method for measuring the gradient of
a brightness curve for evaluation of the gradient of the brightness
curve.
[0075] FIG. 4a is a SEM observation photograph of the copper foil
surface in Example B3-1 for evaluating Rz.
[0076] FIG. 4b is a SEM observation photograph of the copper foil
surface in Example A3-1 for evaluating Rz.
[0077] FIG. 4c is a SEM observation photograph of the copper foil
surface in Example A3-2 for evaluating Rz.
[0078] FIG. 4d is a SEM observation photograph of the copper foil
surface in Example A3-3 for evaluating Rz.
[0079] FIG. 4e is a SEM observation photograph of the copper foil
surface in Example A3-4 for evaluating Rz.
[0080] FIG. 4f is a SEM observation photograph of the copper foil
surface in Example A3-5 for evaluating Rz.
[0081] FIG. 4g is a SEM observation photograph of the copper foil
surface in Example A3-6 for evaluating Rz.
[0082] FIG. 4h is a SEM observation photograph of the copper foil
surface in Example A3-7 for evaluating Rz.
[0083] FIG. 4i is a SEM observation photograph of the copper foil
surface in Example A3-8 for evaluating Rz.
[0084] FIG. 4j is a SEM observation photograph of the copper foil
surface in Example A3-9 for evaluating Rz.
[0085] FIG. 4k is a SEM observation photograph of the copper foil
surface in Example B4-2 for evaluating Rz.
[0086] FIG. 4l is a SEM observation photograph of the copper foil
surface in Example B4-3 for evaluating Rz.
[0087] FIG. 5 is a schematic view of a surface profile of polyimide
(PI) after etching a copper foil for both of a positive skewness
Rsk and a negative skewness Rsk of a copper foil surface.
[0088] FIG. 6 is a photograph of the external appearance of dirt
for use in an Example.
[0089] FIG. 7 is a photograph of the external appearance of dirt
for use in an Example.
DESCRIPTION OF EMBODIMENTS
Aspect of Surface Treated Copper Foil and Manufacturing Method
Thereof
[0090] The copper foil for use in the present invention is
effectively used for a copper foil which is used for manufacturing
a laminate by bonding to a resin substrate so as to be removed by
etching.
[0091] The copper foil for use in the present invention may be any
one of an electrolyte copper foil and a rolled copper foil. The
joint area of a copper foil to be bonded to a resin substrate (in
the present invention, the area is also referred to as "one
surface") may be usually subject to a roughening treatment by
electrodeposition for forming a knotty copper foil surface after
degreasing, in order to improve the peel strength of the copper
foil after lamination. Although an electrolyte copper foil has
irregularities when manufactured, the irregularities can be further
enlarged with roughening treatment for enhancing the projection
portion of the electrolyte copper foil. In the present invention,
the roughening treatment is performed by alloy plating such as
copper-cobalt-nickel alloy plating, copper-nickel-phosphorus alloy
plating and nickel-zinc alloy plating. The roughening treatment can
be preferably performed by copper alloy plating. The copper alloy
plating bath to be used is, for example, preferably a plating bath
including copper and at least one element other than copper, more
preferably a plating bath including copper and at least any one
selected from the group consisting of cobalt, nickel, arsenicum,
tungsten, chromium, zinc, phosphorus, manganese and molybdenum. In
the present invention, the roughening treatment is performed at a
higher current density for a shorter roughening treatment time,
compared with a conventional roughening treatment. Common copper
plating or the like may be performed as a pre-treatment before
roughening in some cases, and common copper plating or the like may
be also performed as a finishing treatment after roughening so as
to prevent the detachment of an electrodeposited material in some
cases.
[0092] Examples of a copper foil of the present invention include a
copper alloy foil which contains at least one element such as Ag,
Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V. With high
concentration of the elements (e.g., 10 mass % or more in total),
the conductivity may be reduced in some cases. The conductivity of
a rolled copper foil is preferably 50% IACS or more, more
preferably 60% IACS or more, further preferably 80% IACS or more.
The copper alloy foil may include the element other than copper in
a total concentration of 0 mass % or more and 50 mass % or less,
0.0001 mass % or more and 40 mass % or less, 0.0005 mass % or more
and 30 mass % or less, or 0.001 mass % or more and 20 mass % or
less.
[0093] One surface of the copper foil for use in the present
invention may be provided with a heat-resistant plating layer
(heat-resistant layer), a rustproof plating layer (rustproof layer)
or a weather-resistant layer, after a roughening treatment or
without a roughening treatment. As a treatment for providing the
surface with a heat-resistant plating layer or a rustproof plating
layer without a roughening treatment, a plating treatment in a Ni
plating bath (1) or a Ni--Zn plating bath (2) under the following
conditions can be used. The balance of a treatment solution for use
in electrolysis, a surface treatment or plating, for use in the
present invention, is water, unless especially noted.
(Ni Plating Bath (1))
[0094] Solution composition: Ni 20 to 30 g/L
[0095] pH: 2 to 3
[0096] Current density: 6 to 7 A/dm.sup.2
[0097] Bath temperature: 35 to 45.degree. C.
[0098] Amount of coulomb: 1.2 to 8.4 As/dm.sup.2
[0099] Plating time: 0.2 to 1.2 sec.
(Ni--Zn Plating Bath (2))
[0100] Solution composition: nickel: 20 to 30 g/L, zinc: 0.5 to 2.5
g/L
[0101] pH: 2 to 3
[0102] Current density: 6 to 7 A/dm.sup.2
[0103] Bath temperature: 35 to 45.degree. C.
[0104] Amount of coulomb: 1.2 to 8.4 As/dm.sup.2
[0105] Plating time: 0.2 to 1.2 sec.
[0106] In the case of providing one surface of the copper foil with
a heat-resistant layer or a rustproof layer by plating (plating
which is neither normal plating nor roughening plating) without a
roughening treatment, the plating is required to be performed at a
higher current density for a shorter plating time, compared with a
conventional case.
[0107] The thickness of a copper foil for use in the present
invention is not specifically limited, including, for example, 1
.mu.m or more, 2 .mu.m or more, 3 .mu.m or more, 5 .mu.m or more,
and, for example, 3,000 .mu.m or less, 1,500 .mu.m or less, 800
.mu.m or less, 300 .mu.m or less, 150 .mu.m or less, 100 .mu.m or
less, 70 .mu.m or less, 50 .mu.m or less, and 40 .mu.m or less.
[0108] The manufacturing conditions of electrolyte copper foil for
use in the present invention are as follows:
<Electrolyte Composition>
[0109] Copper: 90 to 110 g/L;
[0110] Sulfuric acid: 90 to 110 g/L;
[0111] Chlorine: 50 to 100 ppm;
[0112] Leveling agent 1 (bis(3-sulfopropyl)disulfide): 10 to 30
ppm; and
[0113] Leveling agent 2 (amine compound): 10 to 30 ppm.
[0114] The amine compound represented by the following formula may
be used as the above-mentioned amine compound.
##STR00001##
(In the chemical formula, R.sub.1 and R.sub.2 are selected from the
group consisting of a hydroxyalkyl group, an ether group, an aryl
group, an aromatic substituted alkyl group, an unsaturated
hydrocarbon group, and an alkyl group.)
<Manufacturing Conditions>
[0115] Current density: 70 to 100 A/dm.sup.2;
[0116] Electrolyte temperature: 50 to 60.degree. C.;
[0117] Linear velocity of electrolyte: 3 to 5 m/sec; and
[0118] Electrolysis time: 0.5 to 10 min.
[0119] In copper-cobalt-nickel alloy plating as roughening
treatment, electroplating may be performed such that a ternary
alloy layer with deposition amounts of copper of 15 to 40
mg/dm.sup.2, cobalt of 100 to 3000 .mu.g/dm.sup.2, and nickel of 50
to 1500 .mu.g/dm.sup.2 is formed, and is preferably performed such
that a ternary alloy layer with deposition amounts of copper of 15
to 40 mg/dm.sup.2, cobalt of 100 to 3000 .mu.g/dm.sup.2, and nickel
of 100 to 1500 .mu.g/dm.sup.2 is formed. A deposition amount of Co
less than 100 .mu.g/dm.sup.2 may cause degradation of heat
resistance and etching properties in some cases. A deposition
amount of Co more than 3,000 .mu.g/dm.sup.2 is not suitable in the
case that effects of magnetic properties have to be considered,
causing etching stains with reduced acid resistance and chemical
resistance in some cases. A deposition amount of Ni less than 50
.mu.g/dm.sup.2 may cause degradation of heat resistance. On the
other hand, a deposition amount of Ni more than 1,500
.mu.g/dm.sup.2 may increase the amount of etching residue in some
cases. The preferable deposition amount of Co is 1,000 to 2,500
.mu.g/dm.sup.2, and the preferable deposition amount of Nickel is
500 to 1,200 .mu.g/dm.sup.2. In the specification, the presence of
etching stains means that Co remains undissolved in etching with
copper chloride, and the presence of etching residue means that Ni
remains undissolved in alkali etching with ammonium chloride.
[0120] The plating bath and the plating conditions for forming the
ternary copper-cobalt-nickel alloy plating are as follows:
[0121] Plating bath composition: Cu: 10 to 20 g/L, Co: 1 to 10 g/L,
and Ni: 1 to 10 g/L;
[0122] pH: 1 to 4;
[0123] Temperature: 30 to 50.degree. C.;
[0124] Current density D.sub.k: 25 to 50 A/dm.sup.2; and
[0125] Plating time: 0.2 to 3 sec.
[0126] One surface of a surface treated copper foil in an
embodiment of the present invention is roughened under conditions
with a shorter plating time and a higher current density compared
with conventional conditions. The roughening treatment under the
conditions with a shorter plating time and a higher current density
compared with conventional conditions allows finer roughened grains
than conventional grains to be formed on the copper foil surface.
In the case that the plating current density is set to a higher
value in the range, the plating time needs to be set to a lower
value in the range.
[0127] The conditions for copper-nickel-phosphorus alloy plating as
roughening treatment of the present invention are as follows:
[0128] Plating bath composition: Cu: 10 to 50 g/L, Ni: 3 to 20 g/L,
and P: 1 to 10 g/L;
[0129] pH: 1 to 4;
[0130] Temperature: 30 to 40.degree. C.;
[0131] Current density D.sub.k: 30 to 50 A/dm.sup.2; and
[0132] Plating time: 0.2 to 3 sec
[0133] One surface of a surface treated copper foil in an
embodiment of the present invention is roughened under conditions
with a shorter plating time and a higher current density compared
with conventional conditions. The roughening treatment under the
conditions with a shorter plating time and a higher current density
compared with conventional conditions allows finer roughened grains
than conventional grains to be formed on the copper foil surface.
In the case that the plating current density is set to a higher
value in the range, the plating time needs to be set to a lower
value in the range.
[0134] The conditions for copper-nickel-cobalt-tungsten alloy
plating as roughening treatment of the present invention are as
follows:
[0135] Plating bath composition: Cu: 5 to 20 g/L, Ni: 5 to 20 g/L,
Co: 5 to 20 g/L, and W: 1 to 10 g/L;
[0136] pH: 1 to 5;
[0137] Temperature: 30 to 50.degree. C.;
[0138] Current density D.sub.k: 30 to 50 A/dm.sup.2; and
[0139] Plating time: 0.2 to 3 sec.
[0140] One surface of a surface treated copper foil in an
embodiment of the present invention is roughened under conditions
with a shorter plating time and a higher current density compared
with conventional conditions. The roughening treatment under the
conditions with a shorter plating time and a higher current density
compared with conventional conditions allows finer roughened grains
than conventional grains to be formed on the copper foil surface.
In the case that the plating current density is set to a higher
value in the range, the plating time needs to be set to a lower
value in the range.
[0141] The conditions for copper-nickel-molybdenum-phosphorus alloy
plating as roughening treatment of the present invention are as
follows:
[0142] Plating bath composition: Cu: 5 to 20 g/L, Ni: 5 to 20 g/L,
Mo: 1 to 10 g/L, and P: 1 to 10 g/L;
[0143] pH: 1 to 5;
[0144] Temperature: 30 to 50.degree. C.;
[0145] Current density D.sub.k: 30 to 50 A/dm.sup.2; and
[0146] Plating time: 0.2 to 3 sec.
[0147] One surface of a surface treated copper foil in an
embodiment of the present invention is roughened under conditions
with a shorter plating time and a higher current density compared
with conventional conditions. The roughening treatment under the
conditions with a shorter plating time and a higher current density
compared with conventional conditions allows finer roughened grains
than conventional grains to be formed on the copper foil surface.
In the case that the plating current density is set to a higher
value in the range, the plating time needs to be set to a lower
value in the range.
[0148] After roughening treatment, at least one layer selected from
the group consisting of a heat-resistant layer, a rustproof layer
and a weather-resistant layer may also be provided on the
roughening treated surface. Such respective layers may be made of a
plurality of layers such as two layers and three layers, and may be
laminated in any order or may be alternately laminated.
[0149] A known heat-resistant layer can be used as the
heat-resistant layer. For example, the following surface treatment
can be used.
[0150] A known heat-resistant layer and a known rustproof layer can
be used as the heat-resistant layer and the rustproof layer,
respectively. For example, the heat-resistant layer and/or the
rustproof layer may be a layer including at least one element
selected from the group consisting of nickel, zinc, tin, cobalt,
molybdenum, copper, tungsten, phosphorus, arsenicum, chromium,
vanadium, titanium, aluminum, gold, silver, a platinum group
element, iron and tantalum, or may be a metal layer or an alloy
layer made of at least one element selected from the group
consisting of nickel, zinc, tin, cobalt, molybdenum, copper,
tungsten, phosphorus, arsenicum, chromium, vanadium, titanium,
aluminum, gold, silver, a platinum group element, iron and
tantalum. The heat-resistant layer and/or the rustproof layer may
include an oxide, a nitride, or a silicide including at least one
element selected from the group consisting of nickel, zinc, tin,
cobalt, molybdenum, copper, tungsten, phosphorus, arsenicum,
chromium, vanadium, titanium, aluminum, gold, silver, a platinum
group element, iron and tantalum. The heat-resistant layer and/or
the rustproof layer may be a layer including a nickel-zinc alloy.
The heat-resistant layer and/or the rustproof layer may be a
nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50
wt % to 99 wt % of nickel and 50 wt % to 1 wt % of zinc, excluding
unavoidable impurities. The total deposition amount of zinc and
nickel in the nickel-zinc alloy layer may be 5 to 1000 mg/m.sup.2,
preferably 10 to 500 mg/m.sup.2, preferably 20 to 100 mg/m.sup.2.
The ratio of the deposition amount of nickel to the deposition
amount of zinc (=deposition amount of nickel/deposition amount of
zinc) in the layer including a nickel-zinc alloy or the nickel-zinc
alloy layer is preferably 1.5 to 10. The deposition amount of
nickel in the layer including a nickel-zinc alloy or the
nickel-zinc alloy layer is preferably 0.5 mg/m.sup.2 to 500
mg/m.sup.2, more preferably 1 mg/m.sup.2 to 50 mg/m.sup.2. When the
heat-resistant layer and/or the rustproof layer is the layer
including a nickel-zinc alloy, the interface between the copper
foil and the resin substrate is hardly eroded by a desmear liquid
in contacting of an inner wall portion such as a through-hole and a
via hole with a desmear liquid, resulting in an improvement in
adhesion properties of the copper foil and the resin substrate. The
rustproof layer may be a chromate treated layer. A known chromate
treated layer can be used as the chromate treated layer. For
example, the chromate treated layer refers to as a layer treated
with a solution including chromic anhydride, chromic acid,
dichromic acid, a chromic acid salt or a dichromic acid salt. The
chromate treated layer may include an element such as cobalt, iron,
nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus,
tungsten, tin, arsenicum and titanium (which may be in the form of
any of metal, alloy, oxide, nitride, sulfide, and the like).
Specific examples of the chromate treated layer include a pure
chromate treated layer and a zinc chromate treated layer. In the
present invention, a chromate treated layer treated with chromic
anhydride or an aqueous potassium dichromate solution is referred
to as a pure chromate treated layer. In the present invention, a
chromate treated layer treated with a treatment solution including
chromic anhydride or potassium dichromate and zinc is referred to
as a zinc chromate treated layer.
[0151] For example, the heat-resistant layer and/or the rustproof
layer may be one in which a nickel or nickel alloy layer with a
deposition amount of 1 mg/m.sup.2 to 100 mg/m.sup.2, preferably 5
mg/m.sup.2 to 50 mg/m.sup.2, and a tin later with a deposition
amount of 1 mg/m.sup.2 to 80 mg/m.sup.2, preferably 5 mg/m.sup.2 to
40 mg/m.sup.2 are sequentially laminated, and the nickel alloy
layer may be configured from any one of nickel-molybdenum,
nickel-zinc and nickel-molybdenum-cobalt. In the heat-resistant
layer and/or the rustproof layer, the total deposition amount of
nickel or a nickel alloy and tin is preferably 2 mg/m.sup.2 to 150
mg/m.sup.2, more preferably 10 mg/m.sup.2 to 70 mg/m.sup.2. In the
heat-resistant layer and/or the rustproof layer, the [deposition
amount of nickel in the nickel or nickel alloy]/[the deposition
amount of tin] is 0.25 to 10, more preferably 0.33 to 3.
[0152] A cobalt-nickel alloy plating layer having deposition
amounts of cobalt of 200 to 2000 .mu.g/dm.sup.2 and nickel of 50 to
700 .mu.g/dm.sup.2 may be formed as the heat-resistant layer and/or
the rustproof layer. This treatment can be regarded as a kind of
rustproof treatment in a broad sense. The cobalt-nickel alloy
plating layer needs to be formed to an extent not to substantially
reduce the adhesion strength between the copper foil and the
substrate. A deposition amount of cobalt less than 200
.mu.g/dm.sup.2 may cause reduction of heat resistant peel strength
with degraded oxidation resistance and chemical resistance in some
cases. In addition, another reason that a small amount of cobalt is
not preferred is that the treated surface has a reddish color.
[0153] After the roughening treatment, a cobalt-nickel alloy
plating layer having deposition amounts of cobalt of 200 to 3,000
.mu.g/dm.sup.2 and nickel of 100 to 700 .mu.g/dm.sup.2 on the
roughened surface may be formed. This treatment can be regarded as
a kind of rustproof treatment in a broad sense. The cobalt-nickel
alloy plating layer needs to be formed to an extent not to
substantially reduce the adhesion strength between the copper foil
and the substrate. A deposition amount of cobalt less than 200
.mu.g/dm.sup.2 may cause reduction of heat resistant peel strength
with degraded oxidation resistance and chemical resistance in some
cases. In addition, another reason that a small amount of cobalt is
not preferred is that the treated surface has a reddish color. A
deposition amount of cobalt more than 3,000 .mu.g/dm.sup.2 is not
suitable in the case that effects of magnetic properties have to be
considered, causing etching stains with reduced acid resistance and
chemical resistance in some cases. The preferable deposition amount
of cobalt is 500 to 2,500 .mu.g/dm.sup.2. On the other hand, a
deposition amount of nickel less than 100 .mu.g/dm.sup.2 may cause
reduction of heat resistant peel strength with degraded oxidation
resistance and chemical resistance in some cases. An amount of
nickel more than 1,300 .mu.g/dm.sup.2 results in poor alkali
etching properties. The preferable deposition amount of nickel is
200 to 1,200 .mu.g/dm.sup.2.
[0154] The condition for cobalt-nickel alloy plating is as
follows:
[0155] Plating bath composition: Co: 1 to 20 g/L and Ni: 1 to 20
g/L;
[0156] pH: 1.5 to 3.5;
[0157] Temperature: 30 to 80.degree. C.;
[0158] Current density D.sub.k: 1.0 to 20.0 A/dm.sup.2; and
[0159] Plating time: 0.5 to 4 sec.
[0160] According to the present invention, a zinc plating layer
with a deposition amount of 30 to 250 .mu.g/dm.sup.2 is further
formed on a cobalt-nickel alloy plating layer. A deposition amount
of zinc less than 30 .mu.g/dm.sup.2 may eliminate the effect for
improving the degradation rate of heat resistance in some cases. On
the other hand, a deposition amount of zinc more than 250
.mu.g/dm.sup.2 may drastically worsen the degradation rate of
hydrochloric acid resistance in some cases. The deposition amount
of zinc is preferably 30 to 240 .mu.g/dm.sup.2, more preferably 80
to 220 .mu.g/dm.sup.2.
[0161] The conditions for the zinc plating are as follows:
[0162] Plating bath composition: Zn: 100 to 300 g/L;
[0163] pH: 3 to 4;
[0164] Temperature: 50 to 60.degree. C.;
[0165] Current density D.sub.k: 0.1 to 0.5 A/dm.sup.2; and
[0166] Plating time: 1 to 3 sec.
[0167] Alternatively, a plating layer of zinc alloy such as that of
zinc-nickel alloy may be formed instead of the zinc plating layer.
On the outermost surface, a rustproof layer may be further formed
by treatment such as chromating or application of a silane coupling
agent.
[0168] A known weather-resistant layer can be used as the
weather-resistant layer. For example, a known silane coupling
treated layer, or a silane coupling treated layer formed using the
following silane can be used as the weather-resistant layer.
[0169] A known silane coupling agent may be used for the silane
coupling agent for use in a silane coupling treatment, and for
example, an amino-based silane coupling agent, an epoxy-based
silane coupling agent, or a mercapto-based silane coupling agent
may be used. Vinyltrimethoxysilane, vinylphenyltrimethoxysilane,
.gamma.-methacryloxypropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane,
4-glycidylbutyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
N-.beta.(aminoethyl).gamma.-aminopropyltrimethoxysilane,
N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane,
imidazolsilane, triazinesilane,
.gamma.-mercaptopropyltrimethoxysilane or the like may be used for
the silane coupling agent.
[0170] The silane coupling treated layer may be formed with a
silane coupling agent such as epoxy-based silane, amino-based
silane, methacryloxy-based silane and mercapto-based silane. Such a
silane coupling agent may be used as a mixture of two or more. In
particular, a silane coupling treated layer formed with an
amino-based silane coupling agent or an epoxy-based silane coupling
agent is preferable.
[0171] The amino-based silane coupling agent referred herein may be
selected from the group consisting of
N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,
3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,
3-aminopropyltriethoxysilane,
bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane,
aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane,
N-phenylaminopropyltrimethoxysilane,
N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,
4-aminobutyltriethoxysilane,
(aminoethylaminomethyl)phenethyltrimethoxysilane,
N-(2-aminoethyl-3-aminopropyl)trimethoxysilane,
N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexoxy)silane,
6-(aminohexylaminopropyl)trimethoxysilane,
aminophenyltrimethoxysilane,
3-(1-aminopropoxy)-3,3-dimethyl-1-propenyltrimethoxysilane,
3-aminopropyltris(methoxyethoxyethoxy)silane,
3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane,
.omega.-aminoundecyltrimethoxysilane,
3-(2-N-benzylaminoethylaminopropyl)trimethoxysilane,
bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane,
(N,N-diethyl-3-aminopropyl)trimethoxysilane,
(N,N-dimethyl-3-aminopropyl)trimethoxysilane,
N-methylaminopropyltrimethoxysilane,
N-phenylaminopropyltrimethoxysilane,
3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,
.gamma.-aminopropyltriethoxysilane,
N-.beta.(aminoethyl).gamma.-aminopropyltrimethoxysilane and
N-3-(4-(3-aminopropoxy)butoxy)propyl-3-aminopropyltrimethoxysilane.
[0172] The silane coupling treated layer is desirably provided in
the range from 0.05 mg/m.sup.2 to 200 mg/m.sup.2, preferably 0.15
mg/m.sup.2 to 20 mg/m.sup.2, preferably 0.3 mg/m.sup.2 to 2.0
mg/m.sup.2, in terms of a silicon atom. The above range can allow
adhesion properties between the substrate resin and the surface
treated copper foil to be more enhanced.
[0173] The surface treated copper foil of the present invention may
have a configuration in which the surface treatment of one surface
is a roughening treatment, the roughening treated surface has a TD
ten-spot average roughness Rz of 0.30 to 0.80 .mu.m, the roughening
treated surface has an MD glossiness at 60 degrees of 80 to 350%,
and the ratio A/B of the surface area A of the roughened grains to
the area B of the roughened grains shown in the plan view from one
surface side of the copper foil is 1.90 to 2.40. The surface
roughness Rz (1), the glossiness (2) and the grain surface area
ratio (3) of the copper foil having such a configuration are
described below.
[0174] (1) Surface Roughness Rz
[0175] The surface treated copper foil having the configuration
preferably has roughened grains on one surface of the copper foil
by a roughening treatment, and the roughening treated surface
preferably has a TD ten-spot average roughness Rz measured with a
contact roughness measuring tester, of 0.20 to 0.80 .mu.m. Such a
configuration allows for high peel strength with good adhesion to a
resin, and high transparency of the resin after removal of the
copper foil by etching. Consequently alignment of an IC chip to be
mounted with a positioning pattern which is visually recognized
through the resin can be more easily performed. A TD ten-spot
average roughness Rz measured with a contact roughness measuring
tester, less than 0.20 .mu.m, may result in a concern about the
production cost for preparing a super-smooth surface. On the other
hand, a TD ten-spot average roughness Rz measured with a contact
roughness measuring tester, more than 0.80 .mu.m, may allow
irregularities of the resin surface to be enlarged after removal of
the copper foil by etching, which may cause a problem of defect in
transparency of the resin. The TD ten-spot average roughness Rz of
the roughening treated surface, which is measured with a contact
roughness measuring tester, is more preferably 0.30 to 0.70 .mu.m,
still more preferably 0.35 to 0.60 .mu.m, still more preferably
0.35 to 0.55 .mu.m, still more preferably 0.35 to 0.50 .mu.m. In
the case that the surface treated copper foil of the present
invention is used in applications where a smaller Rz is needed, the
TD ten-spot average roughness Rz of the roughening treated surface
of the surface treated copper foil of the present invention, which
is measured with a contact roughness measuring tester, is
preferably 0.20 to 0.70 .mu.m, more preferably 0.25 to 0.60 .mu.m,
still more preferably 0.30 to 0.60 .mu.m, still more preferably
0.30 to 0.55 .mu.m, still more preferably 0.30 to 0.50 .mu.m.
[0176] "Roughening treated surface" in the surface treated copper
foil of the present invention refers to a surface of the surface
treated copper foil, which is surface treated for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer
and the like after being roughening treated, in the case that such
a surface treatment is performed.
[0177] (2) Glossiness
[0178] The glossiness of the surface treated surface (for example,
roughened surface) of the surface treated copper foil in the
rolling direction (MD) at an incident angle of 60 degrees greatly
affects the transparency of the above-mentioned resin. That is, the
higher the glossiness of the copper foil of the surface treated
surface (for example, roughened surface) is, the better
transparency of the resin is achieved. Consequently, the surface
treated copper foil having the configuration preferably has a
glossiness of one surface of 76 to 350%, preferably 80 to 350%,
more preferably 90 to 300%, still more preferably 90 to 250%, still
more preferably 100 to 250%.
[0179] The MD glossiness and the TD surface roughness Rz of one
surface of the copper foil before surface treatment can be
controlled to thereby control the Sv and the .DELTA.B in the
present invention. The TD glossiness and the TD surface roughness
Rz of one surface of the copper foil before surface treatment can
also be controlled to thereby control the Sv, the Rsk, the Rq and
the ratio E/G in the present invention.
[0180] Specifically, when one surface of the copper foil has a TD
surface roughness (Rz) of 0.30 to 0.80 .mu.m, preferably 0.30 to
0.50 .mu.m and a glossiness in the rolling direction (MD) at an
incident angle of 60 degrees of 350 to 800%, preferably 500 to
800%, before the surface treatment, and furthermore the current
density is higher and the roughening treatment time is shorter than
those in a conventional roughening treatment, the glossiness of the
surface treated copper foil after the surface treatment in the
rolling direction (MD) at an incident angle of 60 degrees is 90 to
350%. The Sv and the .DELTA.B can be controlled to predetermined
values. Such a copper foil can be made by rolling with adjustment
of the oil film equivalent of a rolling oil (high gloss rolling),
chemical polishing such as chemical etching, or electrolytic
polishing in a phosphoric acid solution. Since the TD surface
roughness (Rz) and the MD glossiness of the copper foil are thus
controlled to be in the range before the surface treatment, the
surface roughness (Rz), the surface area, the Sv and the .DELTA.B
of the copper foil after the treatment can be easily controlled. In
the case that the surface roughness (Rz) of the copper foil after
the surface treatment is demanded to be decreased (for example,
Rz=0.20 .mu.m), the treated surface of the copper foil before the
surface treatment preferably has a TD roughness (Rz) of 0.18 to
0.80 .mu.m, preferably 0.25 to 0.50 .mu.m and a glossiness in the
rolling direction (MD) at an incident angle of 60 degrees of 350 to
800%, preferably 500 to 800%, and furthermore the current density
is higher and the roughening treatment time is shorter than those
in a conventional roughening treatment.
[0181] The copper foil before roughening treatment preferably has
an MD glossiness of one surface at 60 degrees of 500 to 800%, more
preferably 501 to 800%, still more preferably 510 to 750%. An MD
glossiness of the copper foil before roughening treatment at 60
degrees, less than 500%, may cause defect in transparency of the
resin compared with the case of 500% or more, and an MD glossiness
more than 800% may cause a problem of difficulty in
manufacturing.
[0182] The high gloss rolling may be performed with an oil film
equivalent defined by the following expression of 13000 to 24000 or
less. If the surface roughness (Rz) of the copper foil after the
surface treatment is demanded to be decreased (for example, Rz=0.20
.mu.m), the high gloss rolling is performed with an oil film
equivalent defined by the following expression of 12000 or more and
24000 or less.
Oil film equivalent={(rolling oil viscosity [cSt]).times.(sheet
passage rate [mpm]+roll circumferential rate [mpm])}/{(roll biting
angle [rad]).times.(material yield stress [kg/mm.sup.2])}
[0183] The rolling oil viscosity [cSt] is kinetic viscosity at
40.degree. C.
[0184] In order to control the oil film equivalent to be 13000 to
24000, a known method may be used such as use of a low-viscosity
rolling oil or slowing down of sheet passage rate.
[0185] Chemical polishing is performed with an etching solution of
sulfuric acid-hydrogen peroxide-water or ammonia-hydrogen
peroxide-water with a concentration lower than normal, for an
extended period of time.
[0186] The control method is also the same as the case that the
roughening treatment is not performed and the heat-resistant layer
or the rustproof layer is provided on the copper foil by plating
(plating which is neither normal plating nor roughening
plating).
[0187] The treated surface, for example, the roughening treated
surface preferably has a ratio F of the MD glossiness at 60 degrees
to the TD glossiness at 60 degrees (F=(MD glossiness at 60
degrees)/(TD glossiness at 60 degrees)), in one surface of the
surface treated copper foil, of 0.80 to 1.40. A ratio F of the MD
glossiness at 60 degrees to the TD glossiness at 60 degrees of the
roughening treated surface, less than 0.80, may cause reduction of
transparency of the resin compared with the case of 0.80 or more. A
ratio F more than 1.40 may cause reduction of transparency of the
resin compared with the case of 1.40 or less. The ratio F is more
preferably 0.90 to 1.35, still more preferably 1.00 to 1.30.
[0188] (3) Surface Area Ratio of Grains
[0189] The ratio A/B of the surface area A of the roughened grains
to the area B of the roughened grains shown in the plan view from
one surface side of the surface treated copper foil, in one surface
of the surface treated copper foil, greatly affects transparency of
the resin. That is, the same surface roughness Rz allows
transparency of the resin to be better as the ratio A/B of the
copper foil is smaller. Consequently, the surface treated copper
foil having the configuration preferably has a ratio A/B of 1.90 to
2.40, more preferably 2.00 to 2.20, in the one surface.
[0190] The morphology and the packing density of grains are
determined by control of the current density and plating time
during grain formation, so that the surface roughness Rz, the
glossiness, and the surface area ratio A/B in the one surface can
be controlled.
[0191] As described above, one surface of the surface treated
copper foil is controlled so as to have a ratio A/B of the surface
area A of the roughened grains to the area B of the roughened
grains shown in the plan view from one surface side of the copper
foil of 1.90 to 2.40, to have enlarged surface irregularities, and
the roughening treated surface is controlled so as to have a TD
ten-spot average roughness Rz of 0.30 to 0.80 .mu.m, to eliminate
an extremely roughened portion on the surface, while the glossiness
of the roughening treated surface can be increased to 80 to 350%.
Such control can allow one surface of the surface treated copper
foil of the present invention to have a small roughened grain size
on the roughening treated surface. While the roughened grain size
affects transparency of the resin after removal of the copper foil
by etching, such control means reduction of the roughened grain
size within an appropriate range, thereby resulting in better
transparency of the resin after removal of the copper foil by
etching, and also better peel strength.
[0192] As described above, one surface of the surface treated
copper foil is controlled so as to have a ratio A/B of the surface
area A of the roughened grains to the area B of the roughened
grains shown in the plan view from one surface side of the copper
foil of 1.90 to 2.40, to have enlarged surface irregularities, and
the roughening treated surface is controlled so as to have a TD
ten-spot average roughness Rz of 0.30 to 0.80 .mu.m, to eliminate
an extremely roughened portion on the surface, while the glossiness
of the roughening treated surface can be increased to 80 to 350%.
Such control can allow one surface of the surface treated copper
foil of the present invention to have a small roughened grain size
on the roughening treated surface. While the roughened grain size
affects transparency of the resin after removal of the copper foil
by etching, such control means reduction of the roughened grain
size within an appropriate range, thereby resulting in better
transparency of the resin after removal of the copper foil by
etching, and also better peel strength.
[0193] [Root Mean Square Height Rq of Copper Foil Surface]
[0194] In the surface treated copper foil of the present invention,
the root mean square height Rq of one surface is preferably
controlled to be 0.14 to 0.63 .mu.m. Such a configuration allows
for high peel strength with good adhesion to a resin, and high
transparency of the resin after removal of the copper foil by
etching. Consequently alignment of an IC chip to be mounted with a
positioning pattern which is visually recognized through the resin
can be more easily performed. A root mean square height Rq less
than 0.14 .mu.m results in an insufficient roughening treatment of
the copper foil surface, which causes a problem of insufficient
adhesion to the resin. On the other hand, a root mean square height
Rq of one surface more than 0.63 .mu.m allows irregularities of the
resin surface to be enlarged after removal of the copper foil by
etching, which causes a problem of defect in transparency of the
resin. The root mean square height Rq of the roughening treated
surface is more preferably 0.25 to 0.60 .mu.m, still more
preferably 0.32 to 0.56 .mu.m.
[0195] The root mean square height Rq of a surface is an index for
representing the degree of irregularities in surface roughness
measurement with a non-contact roughness measuring tester in
accordance with JIS B 0601 (2001), being represented by the
following expression, which is a height of irregularities (peaks)
of the surface roughness in the Z-axis direction, and the root mean
square of the peak height Z(x) in the reference length lr.
[0196] The root mean square height Rq of the peak height in the
reference length lr:
{(1/lr).times..intg.Z.sup.2(x)dx
(wherein the integral represents the integrated value from 0 to
lr)}
[0197] The root mean square height Rq of a surface is controlled as
follows. In the case of a non-roughened surface treated surface,
the treatment is performed with a low current density such that no
irregularities are formed on a plating film as described above. In
the case of a roughening treated surface, the treatment is
performed with a high current density. Roughened grains are thus
down-sized, and a surface with small roughness can be formed with a
reduced plating time.
(Skewness Rsk of Copper Foil Surface)
[0198] The skewness Rsk represents the cubic mean of Z(x) in a
dimensionless reference length as the cube of root mean square
height Rq.
[0199] The root mean square height Rq is an index for representing
the degree of irregularities in surface roughness measurement with
a non-contact roughness measuring tester in accordance with JIS B
0601 (2001), being represented by the following expression (A),
which is a height of irregularities (peaks) of the surface
roughness in the Z-axis direction, and the root mean square of the
peak height Z(x) in the reference length lr.
[0200] The root mean square height of the peak height in the
reference length lr:
[ Expression 1 ] Rq = 1 lr .intg. 0 lr Z 2 ( x ) x ( A )
##EQU00001##
[0201] The skewness Rsk is represented by the following expression
(B), using the root mean square height Rq.
[ Expression 2 ] Rsk = 1 Rq 3 1 lr .intg. 0 lr Z 3 ( x ) x ( B )
##EQU00002##
[0202] The skewness Rsk of a copper foil surface is an index for
representing symmetry of the irregularities on the copper foil
surface relative to the averaged surface as the center of a surface
with irregularities of the copper foil surface. As shown in FIG. 5,
in the case of Rsk<0, the height distribution is biased to the
upper side relative to the averaged surface, while in the case of
Rsk>0, the height distribution is biased to the lower side
relative to the averaged surface. With a large bias to the upper
side, the polyimide (PI) surface in a concave shape is formed when
the copper foil is removed by etching after being attached to the
PI, enhancing diffused reflection inside the PI when irradiated
with light from a light source. With a large bias to the lower
side, the polyimide (PI) surface in a convex shape is formed when
the copper foil is removed by etching after being attached to the
PI, enhancing diffused reflection at the PI surface when irradiated
with light from a light source.
[0203] One surface of a surface treated copper foil of the present
invention is preferably controlled to have a skewness Rsk of -0.35
to 0.53. Such a configuration allows for high peel strength with
good adhesion to a resin, and high transparency of the resin after
removal of the copper foil by etching. Consequently, the alignment
during mounting an IC chip can be easily performed through a
positioning pattern which is visually recognized through the resin.
A skewness Rsk less than -0.35 may result in an insufficient
surface treatment such as roughening treatment of the copper foil
surface, which causes a problem of insufficient adhesion to the
resin. On the other hand, a skewness Rsk more than 0.53 may allow
irregularities of the resin surface to be enlarged after removal of
the copper foil by etching, which causes a problem of defect in
transparency of the resin. The skewness Rsk of the treated surface
of a copper foil is preferably -0.30 or more, or -0.20 or more and
-0.10 or less. Alternatively, the skewness Rsk of one of the
treated surfaces of a copper foil is preferably 0.15 or more, or
0.20 or more and 0.50 or less, 0.45 or less, or 0.40 or less, or
more preferably 0.39 or less. Alternatively, the skewness Rsk of
the treated surface of a copper foil is preferably -0.30 or more
and 0.50 or less, more preferably 0.39 or less.
[0204] The surface skewness Rsk is controlled as follows. In the
case of a non-roughened surface treated surface, the treatment is
performed with a low current density such that no irregularities
are formed on a plating film as described above. In the case of
roughening treated surface, the treatment is performed with a high
current density. Roughened grains are thus down-sized, and a
surface with small roughness can be formed with a reduced plating
time.
[0205] [Ratio E/G of Projection Portion Volume E to Surface Area G
of Copper Foil Surface]
[0206] One surface of the surface treated copper foil of the
present invention is preferably controlled so as to have a ratio
E/G of the projection portion volume E of a surface to the surface
area G of a surface shown in plan view of 2.11 to 23.91. Such a
configuration allows for high peel strength with good adhesion to a
resin, and high transparency of the resin after removal of the
copper foil by etching. Consequently alignment of an IC chip to be
mounted with a positioning pattern which is visually recognized
through the resin can be more easily performed. A ratio E/G less
than 2.11 .mu.m results in an insufficient roughening treatment of
the copper foil surface, which causes a problem of insufficient
adhesion to the resin. On the other hand, a ratio E/G more than
23.91 .mu.m allows irregularities of the resin surface to be
enlarged after removal of the copper foil by etching, which causes
a problem of defect in transparency of the resin. The ratio E/G is
more preferably 2.95 to 21.42 .mu.m, still more preferably 10.54 to
13.30 .mu.m.
[0207] "Surface area G of a surface shown in plan view" means the
total surface area of a peak portion and a valley portion based on
a certain height (threshold).
[0208] "Projection portion volume E of a surface" means the total
volume of a peak portion and a valley portion based on a certain
height (threshold).
[0209] The ratio E/G of the projection portion volume E of a
surface to the surface area G of a surface is controlled by
adjustment of the current density and the plating time of the
roughened grains as described above. The plating treatment is
performed with a high current density to provide small roughened
grains, and is performed with a low current density to provide
large roughened grains. The number of grains to be formed under
such conditions is determined depending on the plating treatment
time, and the projection portion volume E is thus determined
depending on a combination of the current density and the plating
time.
[0210] [Ten-Spot Average Roughness Rz of Copper Foil Surface]
[0211] The surface treated copper foil of the present invention may
be a non-roughening treated copper foil or a roughening treated
copper foil having roughened grains formed, and the roughening
treated surface preferably has a TD ten-spot average roughness Rz
measured with a contact roughness measuring tester, of 0.20 to 0.64
.mu.m. Such a configuration allows for good adhesion to a resin
with more increased peel strength, improving more the transparency
of the resin after removal of the copper foil by etching.
Consequently alignment of an IC chip to be mounted with a
positioning pattern which is visually recognized through the resin
can be more easily performed. A TD ten-spot average roughness Rz
measured with a contact roughness measuring tester, less than 0.20
.mu.m, may result in an insufficient roughening treatment of the
copper foil surface, which may cause a problem of insufficient
adhesion to the resin. On the other hand, a TD ten-spot average
roughness Rz measured with a contact roughness measuring tester,
more than 0.64 .mu.m, may allow irregularities of the resin surface
to be enlarged after removal of the copper foil by etching, which
may cause a problem of defect in transparency of the resin. The TD
ten-spot average roughness Rz of the treated surface, measured with
a contact roughness measuring tester, is more preferably 0.40 to
0.62 .mu.m, still more preferably 0.46 to 0.55 .mu.m.
[0212] In order to further enhance the visibility effect of the
present invention, the TD roughness (Rz) and the glossiness of one
surface of the copper foil before the surface treatment, measured
with a contact roughness measuring tester, are controlled.
Specifically, the TD (the perpendicular direction (the width
direction of the copper foil) to the rolling direction, in the case
of an electrolyte copper foil, the perpendicular direction to the
passing direction of the copper foil in the manufacturing device of
the electrolyte copper foil) surface roughness (Rz) of one surface
of the copper foil before the surface treatment, measured with a
contact roughness measuring tester, is 0.20 to 0.55 .mu.m,
preferably 0.20 to 0.42 .mu.m. Such a copper foil can be made by
rolling with adjustment of the oil film equivalent of a rolling oil
(high gloss rolling) or adjustment of the surface roughness of a
stretch roll, chemical polishing such as chemical etching, or
electrolytic polishing in a phosphoric acid solution. Since the TD
surface roughness (Rz) of the copper foil before the treatment is
thus controlled within the above range, and the TD glossiness of
the copper foil before the treatment is thus controlled within the
above range, the surface roughness (Rz) of the copper foil after
the treatment, the surface area, the Sv, the Rq, the Rsk, and the
ratio E/G of the projection portion volume E to the surface area G
of the copper foil surface can be controlled.
[0213] One surface of the copper foil before the surface treatment
has a TD glossiness of 400 to 710% at 60 degrees, preferably 500 to
710%. In the case that one surface of a copper foil has an MD
glossiness at 60 degrees less than 400% before the surface
treatment, more defects in transparency of the resin may be caused
compared with the case of 400% or more. In the case of more than
710%, a problem of difficulty in manufacturing may be caused.
[0214] The high gloss rolling may be performed with an oil film
equivalent defined by the following expression of 13,000 to 24,000
or less:
Oil film equivalent={(rolling oil viscosity [cSt]).times.(sheet
passage rate [mpm]+roll circumferential rate [mpm])}/{(roll biting
angle [rad]).times.(material yield stress [kg/mm.sup.2])}
[0215] The rolling oil viscosity [cSt] is kinetic viscosity at
40.degree. C.
[0216] In order to control the oil film equivalent to be 13,000 to
24,000, a known method may be used such as use of a low-viscosity
rolling oil or slowing down of sheet passage rate.
[0217] The surface roughness of the stretch roll can be, for
example, 0.01 to 0.25 .mu.m as the arithmetic average roughness Ra
(JIS B0601). In the case that the arithmetic average roughness Ra
of the stretch roll is large, the TD surface roughness (Rz) of the
copper foil before the surface treatment tends to be increased and
the TD glossiness of one surface of the copper foil before the
surface treatment at 60 degrees tends to be decreased. In the case
that the arithmetic average roughness Ra of the stretch roll is
small, the TD surface roughness (Rz) of the copper foil before the
surface treatment tends to be decreased and the TD glossiness of
one surface of the copper foil before the surface treatment at 60
degrees tends to be increased.
[0218] Chemical polishing is performed with an etching solution of
sulfuric acid-hydrogen peroxide-water or ammonia-hydrogen
peroxide-water with a concentration lower than normal, for an
extended period of time.
(Gradient of Brightness Curve)
[0219] A surface treated copper foil of the present invention
comprises an Sv defined by the expression (1) of 3.5 or more based
on a brightness curve; wherein the brightness curve is obtained,
after laminating the surface treated surface of the copper foil
from one surface side to each of both surfaces of a polyimide
substrate resin, removing the copper foil on each of both surfaces
by etching, placing a printed matter with a linear mark under the
exposed polyimide substrate, and photographing the printed matter
with a CCD camera through the polyimide substrate, from an
observation spot versus brightness graph of measurement results of
the brightness of the photographed image of the printed matter for
the respective observation spots along the direction perpendicular
to the extending direction of the observed linear mark, and the
difference between the top average Bt and the bottom average Bb in
the brightness curve extending from an end of the mark to a portion
without the mark is represented by .DELTA.B (.DELTA.B=Bt-Bb); and
wherein t1 represents a value pointing the position of the
intersection closest to the linear mark among the intersections of
the brightness curve and Bt in the observation spot versus
brightness graph, and t2 represents the intersection closest to the
linear mark among the intersections of the brightness curve and
0.1.DELTA.B in the range from the intersections of the brightness
curve and Bt to a depth of 0.1.DELTA.B with Bt as reference.
Sv=(.DELTA.B.times.0.1)/(t1-t2) (1)
[0220] In the observation position-brightness graph, the transverse
axis represents a position information (pixel.times.0.1) value, and
the vertical axis represents a brightness (gradation) value.
[0221] With reference to drawing, "top average Bt of brightness
curve," "bottom average Bb of brightness curve," and the following
"t1," "t2," and "Sv" are described below.
[0222] In FIG. 1(a) and FIG. 1(b), schematic diagrams for defining
Bt and Bb are shown for a mark having a width of approximately 0.3
mm. In the case of a mark having a width of approximately 0.3 mm,
the brightness curve may be in a V-shape as shown in FIG. 1(a), or
may be in a bottomed shape as shown in FIG. 1(b). In both
instances, "top average Bt of brightness curve" represents the
average of brightness measured at 5 spots at intervals of 30 .mu.m
from a position 50 .mu.m away from the end position of both sides
of a mark (total 10 spots on both sides). On the other hand,
"bottom average Bb of brightness curve" represents the lowest value
of the brightness at the tip of the V-shaped valley for the
brightness curve in a V-shape as shown in FIG. 1(a), and the value
of the central part of the approximately 0.3 mm-width for the
brightness curve in a bottomed shape as shown in FIG. 1(b).
[0223] A mark may have a width of about 0.2 mm, 0.16 mm, or 0.1 mm.
Alternatively, "top average Bt of brightness curve" may represent
the average of brightness measured at 5 spots at intervals of 30
.mu.m from a position 100 .mu.m away, a position 300 .mu.m away, or
a position 500 .mu.m away from the end position of both sides of
the mark (total 10 spots on both sides).
[0224] In FIG. 2, a schematic diagram for defining t1, t2, and Sv
is shown. "t1 (pixel.times.0.1)" represents a value (value in the
transverse axis of the observation spot versus brightness graph)
pointing the intersection closest to the linear mark among the
intersections of the brightness curve and Bt, as well as the
position of the closest intersection. "t2 (pixel.times.0.1)"
represents a value (value in the transverse axis of the observation
spot versus brightness graph) pointing the intersection closest to
the linear mark among the intersections of the brightness curve and
0.1.DELTA.B in the range from the intersections of the brightness
curve and Bt to a depth of 0.1.DELTA.B with Bt as reference, as
well as the position of the closest intersection. On this occasion,
the gradient of the brightness curve represented by the line
connecting t1 and t2 is defined by Sv (gradation/pixel.times.0.1)
calculated from 0.1.DELTA.B in y-axis direction and (t1-t2) in
x-axis direction. One pixel in the transverse axis corresponds to a
length of 10 .mu.m. Sv represents the smaller value obtained by
measurement on both sides of a mark. In the case that a plurality
of "intersections of the brightness curve and Bt" are present due
to instability of the shape of the brightness curve, the
intersection closest to the mark is employed.
[0225] In the image photographed by a CCD camera, a portion having
no mark has high brightness, while the brightness sharply falls
down at the end of a mark. With good visibility of the polyimide
substrate, the falling state of brightness can be clearly observed.
On the other hand, with poor visibility of the polyimide substrate,
the brightness does not drastically fall down from "high" to "low"
at the vicinity of the end of a mark, so that the gradual falling
state results in the unclear falling state of brightness.
[0226] In the present invention based on such finding, the surface
treated copper foil of the present invention is laminated to a
polyimide substrate and removed therefrom, and a marked printed
matter is placed under the polyimide substrate so as to be
photographed with a CCD camera through the polyimide substrate.
From the photographed image of the mark part, an observation spot
versus brightness graph is obtained and the gradient of the
brightness curve in the vicinity of the end of a mark is
controlled. More specifically, when the difference between the top
average Bt and the bottom average Bb of the brightness curve is
represented by .DELTA.B (.DELTA.B=Bt-Bb), t1 represents a value
(value in the transverse axis of the observation spot versus
brightness graph) pointing the position of the intersection closest
to the linear mark among the intersections of the brightness curve
and Bt in the observation spot versus brightness graph, and t2
represents a value (value in the transverse axis of the observation
spot versus brightness graph) pointing the position of the
intersection closest to the linear mark among the intersections of
the brightness curve and 0.1.DELTA.B in the range from the
intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference, the Sv defined by the expression
(1) is 3.5 or more. Such a configuration allows the mark to have
improved discriminating power with a CCD camera through the
polyimide without influence of the type and the thickness of a
substrate resin. A polyimide substrate having excellent visibility
can be thus manufactured. Consequently positioning accuracy by
marking is improved in a predetermined processing of a polyimide
substrate in a step for manufacturing an electronic substrate or
the like. The effects such as improved yields are thus obtained. Sv
is preferably 3.9 or more, more preferably 4.5 or more, still more
preferably 5.0 or more, and still more preferably 5.5 or more.
Although it is not needed to specify the upper limit of Sv, which
may be, for example, 70 or less, 30 or less, 15 or less, or 10 or
less. Such a configuration allows for a clearer boundary between a
mark and a portion other than a mark, improving positioning
accuracy with less error in mark image recognition. More accurate
alignment is thus achieved.
(Surface Area Ratio of Copper Foil Surface)
[0227] The ratio D/C of the three dimensional surface area D on one
surface of a copper foil to the two dimensional surface area C
greatly affects the transparency of the above-mentioned resin.
Namely, for the same surface roughness Rz, the smaller the ratio
D/C of a copper foil, the better transparency of the resin is
achieved. Consequently, the ratio D/C of the surface treated copper
foil of the present invention is preferably 1.0 to 1.7, more
preferably 1.0 to 1.6. In the specification, the ratio D/C of the
three dimensional surface area D on the side of the surface treated
surface to the two dimensional surface area C can be, for example,
in the case of roughening treated surface, the ratio D/C of the
surface area D of roughened grains to the area C of the copper foil
shown in the plan view from the copper foil surface side.
[0228] The surface state of the copper foil after the surface
treatment, and the morphology and the packing density of roughened
grains are determined by control of the current density and the
plating time of the surface treatment during the surface treatment
such as roughened grain formation, so that the surface roughness
Rz, the glossiness, the surface area ratio D/C of the copper foil,
the Sv, the .DELTA.B, the Rq, the Rsk, and the ratio E/G of the
projection portion volume E to the surface area G of the copper
foil can be controlled.
[0229] [Etching Factor]
[0230] In the case that the etching factor value in formation of a
circuit by use of a copper foil is large, a skirting portion of the
circuit bottom, caused in etching, is small and the space between
circuits can be narrow. Consequently, a larger etching factor value
is preferable because of being suitable for circuit formation by a
fine pattern. The surface treated copper foil of the present
invention preferably has, for example, an etching factor value of
1.8 or more, preferably 2.0 or more, preferably 2.2 or more,
preferably 2.3 or more, more preferably 2.4 or more.
[0231] With respect to the printed wiring board or the copper clad
laminate, the grain area ratio (A/B), the glossiness, the surface
roughness Rz, the Sv, the .DELTA.B, the Rq, the Rsk, and the ratio
E/G of the projection portion volume E to the surface area G of the
copper circuit or the copper foil surface can be measured after the
resin is molten and removed.
[0232] [Transmission Loss]
[0233] In the case of a small transmission loss, signal attenuation
in signal transmission at a high frequency is suppressed, and
stable signal transmission can be thus performed in a circuit where
signal transmission is performed at a high frequency. Consequently,
a smaller transmission loss value is preferable because of being
suitable for use in circuit applications where signal transmission
is performed at a high frequency. After lamination of the surface
treated copper foil and a commercially available liquid crystal
polymer resin (Vecstar CTZ-50 .mu.m made by Kuraray Co., Ltd.), a
microstripline is formed by etching such that the characteristic
impedance is 50.OMEGA., the permeation coefficient is measured with
a network analyzer HP8720C made by HP Development Company, L.P.,
and the transmission loss is determined at a frequency of 20 GHz.
The transmission loss at a frequency of 20 GHz is preferably less
than 5.0 dB/10 cm, more preferably less than 4.1 dB/10 cm, still
more preferably less than 3.7 dB/10 cm.
[0234] In the surface treated copper foil of the present invention,
a surface opposite to the joint area of a copper foil to be bonded
to a resin substrate (in the present invention, the surface is also
referred to as "other surface") is also surface treated. In
lamination of one surface of the surface treated copper foil to the
resin substrate, the resin substrate, the surface treated copper
foil and a protective film is generally laminated in this order,
and laminated by a laminate roll under application of heat and
pressure to the protective film. The following problem may be here
caused: the protective film is attached to the surface (other
surface) opposite to the resin substrate, of the surface treated
copper foil (sliding between the surface treated copper foil and
the protective film is not made). Such a problem may be caused to
result in wrinkles and stripes on other surface of the copper foil.
On the contrary, in the present invention, the other surface of the
copper foil, otherwise not surface treated, is surface treated. The
contact area between the copper foil and the protective film is
increased, and the problem of attachment of the protective film to
the copper foil in lamination to the resin substrate can be thus
well suppressed.
[0235] In an aspect of the surface treated copper foil of the
present invention, other surface of the treated copper foil surface
has a TD ten-spot average roughness Rz measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.35
.mu.m or more. Such a configuration allows for a more increased
contact area between the copper foil and the protective film, and
the problem of attachment of the protective film to the copper foil
in lamination to the resin substrate can be thus well suppressed.
In the surface treated copper foil of the present invention, other
surface of the treated copper foil surface more preferably has a TD
ten-spot average roughness Rz measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.40 .mu.m or
more, still more preferably 0.50 .mu.m or more, still more
preferably 0.60 .mu.m or more, still more preferably 0.8 .mu.m or
more, typically 0.40 to 4.0 .mu.m, more typically 0.50 to 3.0
.mu.m. In the surface treated copper foil of the present invention,
although it is not needed to particularly specify the upper limit
of the TD ten-spot average roughness Rz measured with a laser
microscope using laser light having a wavelength of 405 nm, of
other surface of the treated copper foil surface, the upper limit
may be typically 4.0 .mu.m or less, more typically 3.0 .mu.m or
less, more typically 2.5 .mu.m or less, more typically 2.0 .mu.m or
less.
[0236] In another aspect of the surface treated copper foil of the
present invention, other surface of the treated copper foil surface
has a TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.05
.mu.m or more. Such a configuration allows for a more increased
contact area between the copper foil and the protective film, and
the problem of attachment of the protective film to the copper foil
in lamination to the resin substrate can be thus well suppressed.
In the surface treated copper foil of the present invention, other
surface of the treated copper foil surface more preferably has a TD
arithmetic average roughness Ra measured with a laser microscope
using laser light having a wavelength of 405 nm, of 0.08 .mu.m or
more, still more preferably 0.10 .mu.m or more, still more
preferably 0.20 .mu.m or more, still more preferably 0.30 .mu.m or
more. In the surface treated copper foil of the present invention,
although it is not needed to particularly specify the upper limit
of the TD arithmetic average roughness Ra measured with a laser
microscope using laser light having a wavelength of 405 nm, of
other surface of the treated copper foil surface, the upper limit
may be typically 0.80 .mu.m or less, more typically 0.65 .mu.m or
less, more typically 0.50 .mu.m or less, more typically 0.40 .mu.m
or less.
[0237] In further another aspect of the surface treated copper foil
of the present invention, other surface of the treated copper foil
surface has a TD root mean square height Rq measured with a laser
microscope using laser light having a wavelength of 405 nm, of 0.08
.mu.m or more. Such a configuration allows for a more increased
contact area between the copper foil and the protective film, and
the problem of attachment of the protective film to the copper foil
in lamination to the resin substrate can be thus well suppressed.
In the surface treated copper foil of the present invention, other
surface of the treated copper foil surface more preferably has a TD
root mean square height Rq measured with a laser microscope using
laser light having a wavelength of 405 nm, of 0.10 .mu.m or more,
still more preferably 0.15 .mu.m or more, still more preferably
0.20 .mu.m or more, still more preferably 0.30 .mu.m or more,
typically 0.08 to 0.60 .mu.m, more typically 0.10 to 0.50 .mu.m. In
the surface treated copper foil of the present invention, although
it is not needed to particularly specify the upper limit of the TD
root mean square height Rq measured with a laser microscope using
laser light having a wavelength of 405 nm, of the surface treated
other surface of the copper foil, the upper limit may be typically
0.80 .mu.m or less, more typically 0.60 .mu.m or less, more
typically 0.50 .mu.m or less, more typically 0.40 .mu.m or
less.
[0238] The surface treatment of surface treated other surface of
the copper foil of the present invention is not particularly
limited, and may be a roughening treatment, or a treatment where a
roughening treatment is not performed and the heat-resistant layer
or the rustproof layer is provided on the copper foil by plating
(plating which is neither normal plating nor roughening
plating).
[0239] For example, the roughening treatment may be performed with
a plating solution including copper sulfate and a sulfuric acid
aqueous solution, or the roughening treatment may be performed with
a plating solution composed of copper sulfate and a sulfuric acid
aqueous solution. The roughening treatment may also be performed by
alloy plating such as copper-cobalt-nickel alloy plating,
copper-nickel-phosphorus alloy plating and nickel-zinc alloy
plating. The roughening treatment can be preferably performed by
copper alloy plating. As a copper alloy bath, for example,
preferably a plating bath including copper and at least one element
other than copper, more preferably a plating bath including copper
and at least any one selected from the group consisting of cobalt,
nickel, arsenicum, tungsten, chromium, zinc, phosphorus, manganese
and molybdenum is used.
[0240] The surface treatment of surface treated other surface of
the copper foil of the present invention may be a surface treatment
other than the roughening treatment and the plating treatment.
[0241] A surface treatment by electrolytic polishing may be
performed as the surface treatment for forming irregularities on
other surface. For example, irregularities can be formed on other
surface of the copper foil by electrolytic polishing of other
surface of the copper foil in a solution composed of copper sulfate
and a sulfuric acid aqueous solution. While electrolytic polishing
is generally performed for the purpose of smoothing, it is
performed for the contrary purpose to such a usual purpose in the
surface treatment of other surface in the present invention because
irregularities are formed by electrolytic polishing. A method of
forming irregularities by electrolytic polishing may be performed
by a known technique. Such a known electrolytic polishing technique
for forming irregularities includes methods described in Japanese
Patent Laid-Open No. 2005-240132, Japanese Patent Laid-Open No.
2010-059547, and Japanese Patent Laid-Open No. 2010-047842.
Examples of specific conditions of the treatment for forming
irregularities by electrolytic polishing include:
[0242] Treatment solution: Cu: 20 g/L, H.sub.2SO.sub.4: 100 g/L,
temperature: 50.degree. C.
[0243] Electrolytic polishing current: 15 A/dm.sup.2
[0244] Electrolytic polishing time: 15 sec.
[0245] The surface treatment for forming irregularities on other
surface may also form irregularities by, for example, mechanical
polishing of other surface. Such mechanical polishing may be
performed by a known technique.
[0246] After surface treated other surface of the copper foil of
the present invention is surface treated, a heat-resistant layer, a
rustproof layer and a weather-resistant layer may be provided
thereon. The heat-resistant layer, the rustproof layer and the
weather-resistant layer may be provided by the method described
above, a method described in Experimental Examples, or a known
technical method.
[0247] The surface treated copper foil of the present invention can
be laminated to a resin substrate from one surface side so as to
manufacture a laminate. The resin substrate is not specifically
limited so long as having characteristics applicable to a printed
wiring board or the like. For example, a paper base phenolic resin,
a paper base epoxy resin, a synthetic fiber fabric base epoxy
resin, a glass fabric and paper composite base epoxy resin, a glass
fabric and glass nonwoven fabric composite base epoxy resin, or a
glass fabric base epoxy resin can be used for a rigid PWB, while a
polyester film, a polyimide film, a liquid crystal polymer (LCP)
film, or a TEFLON (registered trademark) film can be used for an
FPC.
[0248] In the lamination method for a rigid PWB, a prepreg is
prepared by impregnating a substrate such as glass fabric with a
resin and curing the resin into a semi-cured state. A copper foil
is superimposed on the prepreg so as to be hot pressed from the
side opposite to the coating layer. A laminate for an FPC can be
manufactured by laminating and bonding a copper foil to a substrate
such as a polyimide film through an adhesive or without an adhesive
under high temperature and high pressure, or by the steps of
applying, drying, and curing a polyimide precursor.
[0249] The thickness of a polyimide substrate resin is not
specifically limited. For example, the thickness may be typically
25 .mu.m or 50 .mu.m.
[0250] The laminate of the present invention can be used for
various kinds of printed wiring boards (PWB), and the use is not
specifically limited. For example, in the view of the number of
layers with a conductor pattern, the laminate can be used for a
single-sided PWB, a double-sided PWB, and a multi-layer PWB
(3-layer or more). In the view of the type of insulating substrate
material, the laminate can be used for a rigid PWB, a flexible PWB
(FPC), and a rigid flex PWB.
(Laminate and Positioning Method of Printed Wiring Board Using the
Laminate)
[0251] The positioning method of a laminate of a surface treated
copper foil and a resin substrate of the present invention is
described below. First, a laminate of a surface treated copper foil
and a resin substrate is prepared. Specific examples of the
laminate of a surface treated copper foil and a resin substrate of
the present invention include a laminate for an electronic
apparatus including a main body substrate, an auxiliary circuit
substrate, and a flexible printed substrate for electrically
connecting the above-mentioned substrates, formed of a resin
substrate such as polyimide of which at least one surface is
provided with a copper wiring. The flexible printed substrate is
accurately positioned so as to be pressure bonded to the wiring
terminals of the main body substrate and the auxiliary circuit
substrate. In this case, the laminate is composed of a flexible
printed substrate and a main body substrate of which wiring
terminals are pressure bonded for lamination, or composed of a
flexible printed substrate and a circuit substrate of which wiring
terminals are pressure bonded for lamination. The laminate includes
a mark formed of a part of the copper wiring or another material.
The position of the mark is not specifically limited so long as the
position allows for photographing with photographing means such as
a CCD camera through the resin for constituting the laminate.
[0252] When the mark is photographed with photographing means
through the resin of a laminate thus prepared, the position of the
mark can be well detected. Based on the position of the mark thus
detected, the laminate of the surface treated copper foil and the
resin substrate can be well positioned. In the case of using a
printed wiring board as a laminate, the position of the mark can be
well detected with photographing means by the same positioning
method, so that positioning of the printed wiring board can be more
accurately performed.
[0253] Consequently defects in connection are decreased when a
printed wiring board is connected to another printed wiring board,
so that yield can be increased. Examples of the method for
connecting a printed wiring board to another printed wiring board
include known connecting method such as soldering, connection
through an anisotropic conductive film (ACF), connection through an
anisotropic conductive paste (ACP), and connection through a
conductive adhesive. In the present invention, "a printed wiring
board" includes a printed wiring board mounted with components, a
printed circuit board, and a printed board. Two or more printed
wiring boards of the present invention can be connected so that a
printed wiring board including two or more printed wiring boards
connected to each other can be manufactured. At least one printed
wiring board of the present invention and another printed wiring
board of the present invention or a printed wiring board other than
the printed wiring board of the present invention can be connected
to each other. An electronic apparatus may be manufactured using
such a printed wiring board. In the present invention, "a copper
circuit" includes a copper wiring. A printed wiring board may be
manufactured by connecting the printed wiring board of the present
invention to a component. A printed wiring board having two or more
connected printed wiring boards may be manufactured by connecting
at least one printed wiring board of the present invention to
another printed wiring board of the present invention or to a
printed wiring board other than the printed wiring board of the
present invention, and furthermore connecting a printed wiring
board having two or more of the connected printed wiring boards of
the present invention to a component. "Component" includes an
electronic component such as a connector, LCD (Liquid Cristal
Display), and a glass substrate for use in LCD, an electronic
component (for example, IC chip, LSI chip, VLSI chip and ULSI chip)
comprising semiconductor integrated circuits such as IC (Integrated
Circuit), LSI (Large scale integrated circuit), VLSI (Very Large
scale integrated circuit) and ULSI (Ultra-Large Scale Integrated
circuit), a component for shielding an electronic circuit, and a
component necessary for securing a cover or the like to a printed
wiring board.
[0254] The positioning method according to an embodiment of the
present invention may include a step of transferring a laminate
(including a laminate of a copper foil and a resin substrate and a
printed wiring board). In the step of transferring, transferring
may be performed, for example, with a conveyor such as a belt
conveyor and a chain conveyor, with a transferring device having an
arm mechanism, with a transferring device or transferring means for
transferring a laminate floated by a gas, with a transferring
device or transferring means for transferring a laminate through
rotation of approximately cylindrical matters (including rollers
and bearings), with a transferring device or transferring means
having a hydraulic power source, with a transferring device or
transferring means having a pneumatic power source, with a
transferring device or transferring means having a motor power
source, or with a transferring device or transferring means having
a stage such as a gantry moving type linear guide stage, a gantry
moving type air guide stage, a stack type linear guide stage, and a
linear motor driven stage. Alternatively the transferring step may
be performed with known transferring means.
[0255] The positioning method according to an embodiment of the
present invention may be used in a surface mounting machine and a
chip mounter.
[0256] The laminate of a surface treated copper foil and a resin
substrate to be positioned in the present invention may be a
printed wiring board having a resin board and a circuit arranged on
the resin board. In this case, the mark may be the above-mentioned
circuit.
[0257] In the present invention, "positioning" includes "detecting
the position of a mark or an object." In the present invention,
"alignment" includes "transferring the mark or the object to a
predetermined position on the basis of the detected position after
detection of the position of the mark or the object."
[0258] In the case of a printed wiring board, the circuit on the
printed wiring board may be used as the mark instead of a printed
mark, so that the Sv value can be measured by photographing the
circuit with a CCD camera through the resin. In the case of a
copper clad laminate, a linearly etched copper may be used as the
mark instead of a printed mark, so that the Sv value can be
measured by photographing the linear copper with a CCD camera
through the resin.
[0259] One embodiment of the copper clad laminate of the present
invention is a copper clad laminate having an insulating resin
substrate and a copper foil arranged on the insulating resin
substrate,
wherein the copper foil has one surface facing the insulating resin
substrate and other surface treated surface; and wherein an Sv
defined by the expression (1) is 3.5 or more based on a brightness
curve, wherein the brightness curve is obtained, after etching the
copper foil of the copper clad laminate to provide a linear copper
foil, and photographing the linear copper foil through the
insulating resin substrate with a CCD camera, from an observation
spot versus brightness graph of measurement results of the
brightness of the photographed image of the linear copper foil for
the respective observation spots along the direction perpendicular
to the extending direction of the observed linear copper foil, the
top average and the bottom average in the brightness curve
extending from an end of the linear copper foil to a portion
without the linear copper foil are represented by Bt and Bb,
respectively, and the difference between the top average Bt and the
bottom average Bb is represented by .DELTA.B (.DELTA.B=Bt-Bb), and
wherein t1 represents a value pointing the position of the
intersection closest to the surface treated linear copper foil
among the intersections of the brightness curve and Bt in the
observation spot versus brightness graph, and t2 represents a value
pointing the position of the intersection closest to the surface
treated linear copper foil among the intersections of the
brightness curve and 0.1.DELTA.B in the range from the
intersections of the brightness curve and Bt to a depth of
0.1.DELTA.B with Bt as reference.
[0260] Furthermore, one embodiment of the copper clad laminate of
the present invention is a copper clad laminate configured from an
insulating resin substrate, and a surface treated copper foil, one
surface of which is laminated onto the insulating substrate,
wherein other surface of the copper foil is surface treated; and
wherein an Sv defined by the expression (1) is 3.5 or more based on
a brightness curve: wherein the brightness curve is obtained, after
etching the surface treated copper foil of the copper clad laminate
to provide a surface treated linear copper foil, and photographing
the linear copper foil through the insulating resin substrate, onto
which the one surface is laminated, with a CCD camera, from an
observation spot versus brightness graph of measurement results of
the brightness of the photographed image of the respective
observation spots along the direction perpendicular to the
extending direction of the observed surface treated linear copper
foil, the top average and the bottom average in the brightness
curve extending from an end of the surface treated linear copper
foil to a portion without the surface treated linear copper foil
are represented by Bt and Bb, respectively, and the difference
between the top average Bt and the bottom average Bb is represented
by .DELTA.B (.DELTA.B=Bt-Bb), and wherein t1 represents a value
pointing the position of the intersection closest to the surface
treated linear copper foil among the intersections of the
brightness curve and Bt in the observation spot versus brightness
graph, and t2 represents a value pointing the position of the
intersection closest to the surface treated linear copper foil
among the intersections of the brightness curve and 0.1.DELTA.B in
the range from the intersections of the brightness curve and Bt to
a depth of 0.1.DELTA.B with Bt as reference.
[0261] The surface treated copper foil of the present invention can
be used for the copper foil of the copper clad laminate of the
present invention.
[0262] If such a copper clad laminate is used to manufacture a
printed wiring board, positioning of the printed wiring board can
be more accurately performed. Consequently, defects in connection
are decreased in connection of one printed wiring board to another
printed wiring board, so that yield can be enhanced.
[0263] In the printed wiring board or the copper clad laminate of
the present invention, a surface (other surface) opposite to the
joint area of the copper circuit or the copper foil to be bonded to
the resin substrate is also surface treated. When the printed
wiring board or the copper clad laminate is allowed to pass through
a roll-to-roll manufacturing line, the following problem may be
caused: a transporting roll in the manufacturing line is attached
to (is not slid with) a surface opposite to the resin substrate, of
the printed wiring board or copper clad laminate. If such a problem
is caused, wrinkles and stripes are generated on other surface of
the copper circuit or the copper foil. On the contrary, the other
surface of the printed wiring board or the copper clad laminate of
the present invention is surface treated. The contact area between
the copper circuit or the copper foil and the protective film is
increased, and the problem of attaching to (not sliding with) the
transporting roll in the manufacturing line can be thus well
suppressed. Furthermore, adhesion properties between other surface,
and a dry film and a coverlay is better, and weather resistance of
the printed wiring board or the copper clad laminate is thus
enhanced.
EXAMPLES
Experimental Examples A1-1 to A1-30 and Experimental Examples B1-1
to B1-18
[0264] In Experimental Examples A1-1 to A1-30 and Experimental
Examples B1-1 to B1-18, each copper foil described in Table 2 and
Table 3 was prepared and one surface thereof was plating treated
under conditions described in Table 1 as a roughening
treatment.
[0265] After the roughening plating treatment was performed, a
plating treatment for the next heat-resistant layer and rustproof
layer formation was performed in Experimental Examples A1-1 to
A1-10 and A1-12 to A1-27, and Experimental Examples B1-3, B1-4,
B1-6 and B1-9 to B1-14. Formation conditions of heat-resistant
layer 1 are shown below.
[0266] Solution composition: nickel: 5 to 20 g/L, cobalt: 1 to 8
g/L
[0267] pH: 2 to 3
[0268] Solution temperature: 40 to 60.degree. C.
[0269] Current density: 5 to 20 A/dm.sup.2
[0270] Amount of coulomb: 10 to 20 As/dm.sup.2
[0271] The plating time was set to 0.5 to 2.0 sec.
[0272] Heat-resistant layer 2 was formed on the copper foil on
which heat-resistant layer 1 was applied. Formation conditions of
heat-resistant layer 2 are shown below.
[0273] Solution composition: nickel: 2 to 30 g/L, zinc: 2 to 30
g/L
[0274] pH: 3 to 4
[0275] Solution temperature: 30 to 50.degree. C.
[0276] Current density: 1 to 2 A/dm.sup.2
[0277] Amount of coulomb: 1 to 2 As/dm.sup.2
[0278] In Experimental Examples B1-5, B1-7 and B1-8, the roughening
plating treatment was not performed, and heat-resistant layer 3 was
directly formed on the copper foil prepared. Formation conditions
of heat-resistant layer 3 are shown below.
[0279] Solution composition: nickel: 25 g/L, zinc: 2 g/L
[0280] pH: 2.5
[0281] Solution temperature: 40.degree. C.
[0282] Current density: 6 A/dm.sup.2
[0283] Amount of coulomb: 4.8 As/dm.sup.2
[0284] Plating time: 0.8 sec.
[0285] In Experimental Example B1-15, the roughening plating
treatment was not performed, and heat-resistant layer 4 was
directly formed on the copper foil prepared. Formation conditions
of heat-resistant layer 4 are shown below.
[0286] Solution composition: nickel: 0.3 g/L, zinc: 2.5 g/L,
pyrophosphoric acid bath
[0287] Solution temperature: 40.degree. C.
[0288] Current density: 5 A/dm.sup.2
[0289] Amount of coulomb: 22.5 As/dm.sup.2
[0290] Plating time: 4.5 sec.
[0291] The same surface treatment as in Experimental Example A1-2
was performed in Experimental Example B1-16, the same surface
treatment as in Experimental Example A1-10 was performed in
Experimental Example B1-17, and the same surface treatment as in
Experimental Example A1-11 was performed in Experimental Example
B1-18.
[0292] A rustproof layer was further formed on the copper foil on
which heat-resistant layers 1 and 2, heat-resistant layer 3, or
heat-resistant layer 4 were applied. Formation conditions of the
rustproof layer are shown below.
[0293] Solution composition: potassium dichromate: 1 to 10 g/L,
zinc: 0 to 5 g/L
[0294] pH: 3 to 4
[0295] Solution temperature: 50 to 60.degree. C.
[0296] Current density: 0 to 2 A/dm.sup.2 (for immersion chromate
treatment)
[0297] Amount of coulomb: 0 to 2 As/dm.sup.2 (for immersion
chromate treatment)
[0298] A weather-resistant layer was further formed on the copper
foil on which heat-resistant layers 1 and 2, and the rustproof
layer were applied. Formation conditions are shown below.
[0299] Coating and drying were performed with, as a silane coupling
agent having an amino group,
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (Experimental
Examples A1-17 and A1-24 to A1-27),
N-2-(aminoethyl)-3-aminopropyltriethoxysilane (Experimental
Examples A1-1 to A1-16),
N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (Experimental
Examples A1-18, A1-28, A1-29 and A1-30),
3-aminopropyltrimethoxysilane (Experimental Example A1-19),
3-aminopropyltriethoxysilane (Experimental Examples A1-20 and
A1-21), 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine
(Experimental Example 22), or
N-phenyl-3-aminopropyltrimethoxysilane (Experimental Example
A1-23), to form each weather-resistant layer. Such silane coupling
agents can also be used in combinations of two or more. In
Experimental Examples B1-1 to B1-14, coating and drying were
performed in the same manner with
N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, to form each
weather-resistant layer.
[0300] A rolled copper foil was manufactured as follows. A copper
ingot having each composition shown in Table 2 and Table 3 was
manufactured to be hot rolled. Subsequently, annealing in a
continuous annealing line at 300 to 800.degree. C. and cold rolling
were repeated such that a rolled sheet having a thickness of 1 to 2
mm was produced. The rolled sheet was annealed in a continuous
annealing line at 300 to 800.degree. C. so as to be recrystallized
and finally cold rolled into a copper foil having a thickness
described in Table 2. In Table 2 and Table 3, "tough pitch copper"
described in the column of "type" represents a tough pitch copper
in accordance with the standard JIS H 3100 and JIS C 1100, and
"oxygen-free copper" represents an oxygen-free copper in accordance
with the standard JIS H 3100 and JIS C 1020. "tough pitch
copper+Ag: 100 ppm" means that 100 mass ppm of Ag was added to
tough pitch copper.
[0301] HLP foil made by JX Nippon Mining & Metals Corporation,
was used as the electrolyte copper foil. In the case that
electrolytic polishing or chemical polishing was performed, the
thickness of the foil after electrolytic polishing or chemical
polishing was described.
[0302] In Tables 2 and 3, the key points in the step of
manufacturing a copper foil before surface treatment are described.
"High gloss rolling" means that the final cold rolling (cold
rolling after final recrystallization annealing) was performed at
the described oil film equivalent. "Normal rolling" means that the
final cold rolling (cold rolling after final recrystallization
annealing) was performed at the described oil film equivalent.
"Chemical polishing" and "electrolytic polishing" were performed
under the following conditions.
[0303] "Chemical polishing" was performed with an etching solution
including 1 to 3 mass % of H.sub.2SO.sub.4, 0.05 to 0.15 mass % of
H.sub.2O.sub.2 and the balance of water for a polishing time of 1
hour.
[0304] "Electrolytic polishing" was performed under conditions of
67% of phosphoric acid, 10% of sulfuric acid and 23% of water at a
voltage of 10 V/cm.sup.2 for a time described in Table 2 (when the
electrolytic polishing was performed for 10 sec., the amount of
polishing was 1 to 2 .mu.m.).
Experimental Examples A2-1 to A2-7, B2-1 to B2-2, A3-1 to A3-9,
B3-1 to B3-5, A4-1 to A4-8 and B4-1 to B4-5
[0305] Each copper foil described in Tables 6, 8 and 10 was
prepared and one surface thereof was surface treated under
conditions described in Tables 7, 9 and 11 in Experimental
Examples. A copper foil not roughening treated was also prepared.
"Absent" and "present" in the column of "roughening treatment" in
"surface treatment" mean that the surface treatment was not a
roughening treatment and the surface treatment was a roughening
treatment, respectively.
[0306] A rolled copper foil ("tough pitch copper" in the column of
"type" in Tables representing a rolled copper foil.) was
manufactured as follows. A prescribed copper ingot was manufactured
to be hot rolled. Subsequently, annealing in a continuous annealing
line at 300 to 800.degree. C. and cold rolling were repeated such
that a rolled sheet having a thickness of 1 to 2 mm was produced.
The rolled sheet was annealed in a continuous annealing line at 300
to 800.degree. C. so as to be recrystallized and finally cold
rolled to a copper foil having a final thickness described in Table
1. "Tough pitch copper" in Tables represents a tough pitch copper
in accordance with the standard JIS H 3100 and JIS C 1100.
[0307] In Tables, the key points in the step of manufacturing a
copper foil before surface treatment on one surface are described.
"High gloss rolling" means that the final cold rolling (cold
rolling after final recrystallization annealing) was performed at
the described oil film equivalent. Copper foils having thicknesses
of 6 .mu.m, 12 .mu.m and 35 .mu.m were also produced and evaluated
in Experimental Examples A3-1, A3-2, A4-1 and A4-2. Consequently,
the same results were obtained in the case that the thickness of
the copper foil was 18 .mu.m.
[0308] In predetermined Experimental Examples, other surface of the
copper foil was surface treated as described in Table 12 to Table
15.
[0309] Various evaluations of each sample thus made in Examples
were performed as follows.
[0310] Measurement of Surface Roughness (Rz)
[0311] With regard to the surface treated copper foil in Examples,
the ten-spot average roughness of one surface was measured in
accordance with JIS B 0601-1994 with a contact roughness meter
Surfcorder SE-3C made by Kosaka Laboratory Ltd. The measurement was
performed under the following conditions: measurement reference
length: 0.8 mm; evaluation length: 4 mm; cutoff value: 0.25 mm; and
feed rate: 0.1 mm/s. The measurement position was changed in the
perpendicular direction (TD) to the rolling direction or the
movement direction of an electrolyte copper foil in the
manufacturing device of the electrolyte copper foil, such that the
measurement was performed 10 times, respectively. The value was
obtained from the 10 times measurement.
[0312] The surface roughness (Rz) of the copper foil before surface
treatment was also obtained in the same way, in advance.
[0313] In the case that the copper foil surface was surface treated
for providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, the surface of the surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was used for the measurement.
[0314] The surface roughness of other surface after a surface
treatment in each Experimental Example is preferably measured with
a non-contact type method. Specifically, the surface state of other
surface after a surface treatment in each Experimental Example is
evaluated as a roughness value measured with a laser microscope,
because the surface state can be evaluated in more detail.
[0315] The surface roughness (ten-spot average roughness) Rz of
surface treated other surface of the copper foil was measured with
a laser microscope OLS4000 made by Olympus Corporation in
accordance with JIS B0601 1994. The observation of the copper foil
surface by use of an objective lens with a magnifying power of 50
was performed under conditions of an evaluation length of 258 .mu.m
and a cutoff value of zero. With regard to a rolled copper foil,
the values were measured in the perpendicular direction (TD) to the
rolling direction. With regard to an electrolyte copper foil, the
values were measured in the perpendicular direction (TD) to the
movement direction of the electrolyte copper foil in the
manufacturing device of the electrolyte copper foil. The surface
roughness Rz was measured with the laser microscope at an
environment temperature of 23 to 25.degree. C. The Rz was measured
at any 10 points, and the average of the Rz values at the ten
points was defined as the surface roughness (ten-spot average
roughness) Rz. The wavelength of laser light of the laser
microscope used in the measurement was 405 nm.
[0316] Measurement of Surface Root Mean Square Height Rq;
[0317] The root mean square height Rq of one surface of a copper
foil after a surface treatment in each Experimental Example was
measured with a laser microscope OLS4000 made by Olympus
Corporation. The observation of the copper foil surface with a
magnifying power of 1000 was performed under conditions of an
evaluation length of 647 .mu.m and a cutoff value of zero. With
regard to a rolled copper foil, the values were measured in the
perpendicular direction (TD) to the rolling direction. With regard
to an electrolyte copper foil, the values were measured in the
perpendicular direction (TD) to the movement direction of the
electrolyte copper foil in the manufacturing device of the
electrolyte copper foil. The surface root mean square height Rq was
measured with the laser microscope at an environment temperature of
23 to 25.degree. C.
[0318] Furthermore, the root mean square height Rq of surface
treated other surface of the copper foil was measured with a laser
microscope OLS4000 made by Olympus Corporation in accordance with
JIS B0601 2001. The observation of the copper foil surface by use
of an objective lens with a magnifying power of 50 was performed
under conditions of an evaluation length of 258 .mu.m and a cutoff
value of zero. With regard to a rolled copper foil, the values were
measured in the perpendicular direction (TD) to the rolling
direction. With regard to an electrolyte copper foil, the values
were measured in the perpendicular direction (TD) to the movement
direction of the electrolyte copper foil in the manufacturing
device of the electrolyte copper foil. The surface root mean square
height Rq was measured with the laser microscope at an environment
temperature of 23 to 25.degree. C. The Rq was measured at any 10
points, and the average of the Rq values at the ten points was
defined as the root mean square height Rq. The wavelength of laser
light of the laser microscope used in the measurement was 405
nm.
[0319] Measurement of Surface Skewness Rsk;
[0320] The skewness Rsk of one surface of a copper foil, of the
surface treated surface of a copper foil after a surface treatment
in each Experimental Example, was measured with a laser microscope
OLS4000 made by Olympus Corporation. The Rsk was in accordance with
JIS B0601 2001. The surface observation of a copper foil with a
magnifying power of 1,000 was performed under conditions with an
evaluation length of 647 .mu.m and a cutoff value of zero. With
regard to a rolled copper foil, the values were measured in the
perpendicular direction (TD) to the rolling direction. With regard
to an electrolyte copper foil, the values were measured in the
perpendicular direction (TD) to the movement direction of the
electrolyte copper foil in a manufacturing device of electrolyte
copper foil. The surface skewness Rsk was measured with the laser
microscope at an environment temperature of 23 to 25.degree. C.
[0321] Measurement of Surface Arithmetic Average Roughness Ra;
[0322] The surface roughness Ra of other surface of a copper foil
after a surface treatment in each Experimental Example was measured
with a laser microscope OLS4000 made by Olympus Corporation in
accordance with JIS B0601-1994. The observation of the copper foil
surface by use of an objective lens with a magnifying power of 50
was performed under conditions of an evaluation length of 258 .mu.m
and a cutoff value of zero. With regard to a rolled copper foil,
the values were measured in the perpendicular direction (TD) to the
rolling direction. With regard to an electrolyte copper foil, the
values were measured in the perpendicular direction (TD) to the
movement direction of the electrolyte copper foil in the
manufacturing device of the electrolyte copper foil. The surface
arithmetic average roughness Ra was measured with the laser
microscope at an environment temperature of 23 to 25.degree. C. The
Ra was measured at any 10 points, and the average of the Ra values
at the ten points was defined as the arithmetic average roughness
Ra. The wavelength of laser light of the laser microscope used in
the measurement was 405 nm.
[0323] Measurement of Ratio E/G of Projection Portion Volume E to
Surface Area G of Copper Foil Surface;
[0324] The surface area G of one surface of a copper foil after a
surface treatment in each Experimental Example, shown in plan view,
and the projection portion volume E were measured with a laser
microscope OLS4000 made by Olympus Corporation, and the ratio E/G
was calculated. The value was determined under conditions of an
evaluation area of 647 .mu.m.times.646 .mu.m and a cutoff value of
zero. The surface area G shown in plan view and the projection
portion volume E were measured with the laser microscope at an
environment temperature of 23 to 25.degree. C.
[0325] Area Ratio (D/C);
[0326] The surface area of one surface of a copper foil after a
surface treatment in each Experimental Example was measured with a
laser microscope. The three-dimensional surface area D for an
equivalent area (surface area shown in plan view) C of 647
.mu.m.times.646 .mu.m (417,953 .mu.m.sup.2 in actual data), of the
treated surface of a copper foil after a surface treatment in each
Experimental Example, was measured with a laser microscope OLS4000
made by Olympus Corporation with a magnifying power of 20. The
ratio was calculated by the following expression: three-dimensional
surface area D/two-dimensional surface area C=area ratio (D/C). The
three-dimensional surface area B was measured with the laser
microscope at an environment temperature of 23 to 25.degree. C.
[0327] Grain Area Ratio (A/B);
[0328] The surface area of roughened grains was measured with a
laser microscope. The three-dimensional surface area A for an
equivalent area B of 100.times.100 .mu.m (9982.52 .mu.m.sup.2 in
actual data), of one roughening treated surface, was measured with
a laser microscope VK8500 made by Keyence Corporation with a
magnifying power of 2000, and the ratio was obtained by the
following expression: three-dimensional surface area
A/two-dimensional surface area B=area ratio (A/B). With respect to
a copper foil surface not roughening treated, the measurement was
performed and the ratio was calculated by the following expression:
three-dimensional surface area A/two-dimensional surface area
B=area ratio (A/B).
[0329] In the case that one surface of a copper foil surface was
surface treated for providing a heat-resistant layer, a rustproof
layer, a weather-resistant layer, and the like after the copper
foil surface was roughening treated or not roughening treated, the
surface of the surface treated copper foil after the surface
treatment for providing a heat-resistant layer, a rustproof layer,
a weather-resistant layer, and the like was used for the
measurement.
[0330] Glossiness;
[0331] The glossiness of one surface treated surface (roughened
surface in the case that the surface treatment was a roughening
treatment) was measured with a gloss meter, Handy Gloss Meter PG-1
made by Nippon Denshoku Industries Co., Ltd., in accordance with
JIS Z 8741 in each of the rolling direction (MD, the passing
direction in the case of an electrolyte copper foil) and the
perpendicular direction to the rolling direction (TD, the
perpendicular direction to the passing direction in the case of an
electrolyte copper foil) at an incident angle of 60 degrees. In the
case that one surface of a copper foil was surface treated for
providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, the surface of the surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was used for the measurement. The glossiness of a
copper foil before surface treatment was also determined in the
same manner.
[0332] Gradient of Brightness Curve
[0333] A surface treated copper foil was laminated on each of both
sides of a polyimide film so that a surface treated surface as one
surface thereof faced the polyimide film, and the copper foil was
removed by etching (ferric chloride aqueous solution) so as to form
a sample film.
[0334] In Experimental Examples A1-1 to A1-30 and Experimental
Examples B1-1 to B1-14, as the polyimide film, either
(1) a polyimide film having a thickness of 25 .mu.m or 50 .mu.m
made by Kaneka Corporation [PIXEO (polyimide type: FRS), a
polyimide film provided with an adhesive layer for a copper clad
laminate, a PMDA (pyromellitic anhydride) type polyimide film
(PMDA-ODA (4,4'-diamino diphenyl ether) type polyimide film)], or
(2) a polyimide film having a thickness of 50 .mu.m made by Du
Pont-Toray Co., Ltd. [Kapton (registered trademark), a PMDA
(pyromellitic anhydride) type polyimide film (PMDA-ODA (4,
4'-diamino diphenyl ether) type polyimide film)] was used.
[0335] In Experimental Examples A2-1 to A2-7, B2-1 to B2-2, A3-1 to
A3-9, B3-1 to B3-5, A4-1 to A4-8, and B4-1 to B4-5,
(3) a polyimide film having a thickness of 50 .mu.m made by Kaneka
Corporation [Pixeo for a two-layered copper clad laminate (PIXEO
(polyimide type: FRS), a polyimide film provided with an adhesive
layer for a copper clad laminate, a PMDA (pyromellitic anhydride)
type polyimide film (PMDA-ODA (4,4'-diamino diphenyl ether) type
polyimide film)] was used.
[0336] In evaluation of "visibility (transparency of resin)", "peel
strength (adhesion strength)", "solder heat resistance evaluation",
and "yield" described later, a polyimide film to be laminated on
the surface of a surface treated copper foil according to each
Experimental Example is the same as the polyimide film used in
evaluation of "gradient of brightness curve" described above.
[0337] In the case that one surface of a copper foil was surface
treated for providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, the surface treated copper
foil after the surface treatment for providing a heat-resistant
layer, a rustproof layer, a weather-resistant layer, and the like
was laminated on each of both sides of a polyimide film so that the
one surface treated surface faced the polyimide film, and the
surface treated copper foil was removed by etching (ferric chloride
aqueous solution) so as to form a sample film.
[0338] Subsequently, a printed matter with a linear black mark was
placed under the sample film and the printed matter was
photographed with a CCD camera (a line CCD camera with 8192 pixels)
through the sample film. The brightness of the photographed image
was measured for the respective observation spots along the
direction perpendicular to the extending direction of the observed
linear mark, so that an observation spot versus brightness graph
was made. From the brightness curve extending from an end of the
mark to a portion without the mark, the gradient (angle) was
measured. A schematic diagram illustrating the constitution of a
photographic device and a method for measuring the gradient of the
brightness curve for use in the measurement is shown in FIG. 3.
[0339] The .DELTA.B, t1, t2, and Sv were measured with the
following photographing device as shown in FIG. 2. One pixel in the
transverse axis corresponds to a length of 10 .mu.m.
[0340] A transparent film printed with various kinds of lines or
the like as shown in FIG. 6 as dirt (made by Choyokai Co., Ltd.,
product name: "dirt measuring chart, full size version," product
number: JQA160-20151-1 (made by National Printing Bureau,
Independent Administrative Agency)), which is adopted in both of
JIS P 8208 (1998) (FIG. 1: copy of dirt measuring chart) and JIS P
8145 (2011) (appendix JA (standard): dirt comparison chart for
visual observation method, and Figure JA. 1: copy of dirt
comparison chart for visual observation method), was placed on a
sheet of white gloss paper having a glossiness of 43.0.+-.2, for
use as the "printed matter with a linear black mark".
[0341] The glossiness of the gloss paper was measured with a gloss
meter, Handy Gloss Meter PG-1 made by Nippon Denshoku Industries
Co., Ltd., in accordance with JIS Z 8741 at an incident angle of 60
degrees.
[0342] The photographing device includes a CCD camera, a stage
(white color) on which a polyimide substrate with a marked sheet of
paper (a white gloss paper with a dirt) placed thereunder is
placed, a lighting power source which allows the photographed part
of the polyimide substrate to be irradiated with light, and a
transporting machine (not shown in drawing) which transports the
polyimide substrate for evaluation with a marked sheet of paper
placed thereunder to be photographed onto the stage. The main
specifications of the photographing device are as follows:
[0343] Photographing device: sheet inspection device Mujiken made
by Nireco Corporation;
[0344] Line CCD camera: 8,192 pixels (160 MHz), 1,024 gradation
digital (10-bit);
[0345] Lighting power source: high frequency lighting source (power
unit.times.2); and
[0346] Lighting: fluorescent lamp (30 W, model name: FPL27EX-D,
twin fluorescent lamp).
[0347] A line (width of 0.3 mm) drawn in the dirt in FIG. 6
indicated by arrow was used as the line for measuring above, having
an area of 3.0 mm.sup.2. The viewing field of the line CCD camera
was arranged as shown by dotted lines in FIG. 6.
[0348] In photographing by a line CCD camera, signals were
confirmed in a full scale with 256 gradations, and the lens
aperture was adjusted such that the peak gradation signal of the
spot where no black mark of a printed matter is present is
controlled to be within 230.+-.5 (when the transparent film was
placed on the white gloss paper such that the spot other than the
printed mark on the dirt was measured with a CCD camera from the
transparent film side) in a state that no polyimide film (polyimide
substrate) to be measured was placed. The scanning time of the
camera (time period when the shutter of a camera is open, i.e.,
time period for taking light in) was fixed at 250 .mu.s, and the
aperture of a lens was adjusted to be within the gradations.
[0349] With regard to the brightness shown in FIG. 3, zero means
"black," and a brightness of 255 means "white." The degree of gray
color from "black" to "white" (density of black and white, i.e.,
gray scale) is thus segmented into 256 gradations for
representation.
[0350] Visibility (Transparency of Resin);
[0351] A surface treated copper foil was laminated on each of both
sides of a polyimide film so that a surface treated surface as one
surface thereof faced the polyimide, and the copper foil was
removed by etching (ferric chloride aqueous solution) so as to form
a sample film. In the case that one surface of a copper foil
surface was surface treated for providing a heat-resistant layer, a
rustproof layer, a weather-resistant layer, and the like after
being roughening treated or not roughening treated, the surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was laminated on each of both sides of a polyimide
film so that one surface thereof faced the polyimide, and the
copper foil was removed by etching (ferric chloride aqueous
solution) so as to form a sample film. A printed matter (a black
circle with a diameter of 6 cm) was attached to one surface of the
produced resin layer, and the visibility of the printed matter was
determined through the resin layer from the opposite surface. In
the evaluation, a sample having a clear contour of the black circle
for 90% or more of the circumference length was ranked as
"double-circle," a sample having a clear contour of the black
circle for 80% or more and less than 90% of the circumference
length was ranked "circle" (the above were rated acceptable), and a
sample having a clear contour of the black circle for 0 to less
than 80% of the circumference length or having a broken contour was
ranked "X-mark" (unacceptable).
[0352] Peel Strength (Adhesion Strength)
[0353] In accordance with IPC-TM-650, the normal peel strength was
measured with a tension testing machine Autograph 100. A sample
having a normal peel strength of 0.7 N/mm or higher was determined
to be applicable for use in a laminated substrate. In measuring the
peel strength, a sample including a polyimide film laminated to the
surface treated surface as one surface of a surface treated copper
foil in Experimental Examples of the present invention was used.
The polyimide film was attached and fixed to a hard base material
(a stainless steel plate or a synthetic resin plate (having no
deformation during measurement of peel strength)) with a double
stick tape or an instant adhesive for the measurement. The unit of
the peel strength value in Tables is N/mm.
[0354] Solder Heat Resistance Evaluation;
[0355] A surface treated copper foil was laminated on each of both
sides of a polyimide film so that a surface treated surface as one
surface thereof faced the polyimide. A test coupon of the resulting
double-sided laminate was produced in accordance with JIS C6471.
The produced test coupon was exposed under a high-temperature and
high-humidity environment of 85.degree. C. and 85% RH for 48 hours
and then floated in a solder bath at 300.degree. C. to evaluate
solder heat resistance properties. After the solder heat resistance
test, an interface between a roughening treated surface of the
copper foil and a polyimide resin adhesive surface was observed. A
test coupon where the interface was discolored by swelling in 5% or
more of the copper foil area of the test coupon was ranked as "X
mark" (unacceptable), a test coupon where swelling and
discoloration were observed in less than 5% of the copper foil area
of the test coupon was ranked as "circle", and a test coupon where
swelling and discoloration did not occur at all was ranked as
"double-circle". In the case that a copper foil surface was surface
treated for providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, one surface of a surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was used for the measurement.
[0356] In each Experimental Example, as a polyimide film to be
laminated on a surface treated copper foil,
[0357] (4) a polyimide film provided with a thermosetting adhesive
for lamination [thickness: 50 .mu.m, Upilex made by Ube Industries,
Ltd.) (Upilex (registered trademark)-VT, BPDA
(biphenyltetracarboxylic dianhydride) type (BPDA-PDA
(p-phenylenediamine) type) polyimide resin substrate)] was used for
the solder heat resistance evaluation. The results were the same as
those in the solder heat resistance evaluation using either the
polyimide film (having thickness of 25 .mu.m or 50 .mu.m, made by
Kaneka Corporation) in (1) and (3), or the polyimide film (having
thickness of 50 .mu.m, made by Du Pont-Toray Co., Ltd.) in (2).
[0358] Yield;
[0359] A surface treated copper foil was laminated on each of both
sides of a polyimide film so that a surface treated surface as one
surface thereof faced the polyimide, and the copper foil was etched
(ferric chloride aqueous solution) so as to form an FPC having a
circuit width with an L/S of 30 .mu.m/30 .mu.m. Subsequently the
detection of a 20 .mu.m.times.20 .mu.m square mark was tried
through polyimide with a CCD camera. A mark detectable 9 times or
more out of 10 times was rated as "double-circle," a mark
detectable 7 to 8 times was rated as "circle," a mark detectable 6
times was rated as "triangle," and a mark detectable 5 times or
less was rated as "X-mark." In the case that one surface of a
copper foil was surface treated for providing a heat-resistant
layer, a rustproof layer, a weather-resistant layer, and the like
after being roughening treated or not being roughening treated, one
surface of a surface treated copper foil after the surface
treatment for providing a heat-resistant layer, a rustproof layer,
a weather-resistant layer, and the like was used for the
measurement.
[0360] Circuit Geometry by Etching (Fine Pattern Properties);
[0361] A surface treated copper foil was laminated on each of both
sides of a polyimide film provided with a thermosetting adhesive
for lamination (thickness: 50 .mu.m, Upilex made by Ube Industries,
Ltd.) (Upilex (registered trademark)-VT, BPDA
(biphenyltetracarboxylic dianhydride) type (BPDA-PDA
(p-phenylenediamine) type) polyimide resin substrate)) so that a
surface treated surface as one surface thereof faced the polyimide.
The thickness of a copper foil was required to be uniform among
Examples in order to evaluate fine pattern circuit formability, and
a thickness of a copper foil of 12 .mu.m was a reference level.
That is, in the case that the thickness was more than 12 .mu.m, the
thickness was decreased to a thickness of 12 .mu.m by electrolytic
polishing. On the other hand, in the case that the thickness was
less than 12 .mu.m, the thickness was increased to a thickness of
12 .mu.m by a copper plating treatment. A fine pattern circuit was
printed on one surface of the obtained double-sided laminate with a
process of coating a copper foil glossy surface of the laminate
with a photosensitive resist and exposing the resultant, and an
unnecessary region on the copper foil was subjected to an etching
treatment under the following conditions so as to form a fine
pattern circuit satisfying L/S=20/20 .mu.m. The circuit width here
was set so that the bottom width of a circuit cross section was 20
.mu.m.
(Etching Conditions)
[0362] Device: spray type compact etching device Spray pressure:
0.2 MPa Etching solution: ferric chloride aqueous solution
(specific gravity: 40 Baume) Solution temperature: 50.degree.
C.
[0363] A fine pattern circuit was formed, and then immersed in a
NaOH aqueous solution at 45.degree. C. for 1 minute so as to peel a
photosensitive resist film.
[0364] Calculation of Etching Factor (Ef);
[0365] The fine pattern circuit sample obtained above was observed
from above the circuit with a scanning electron microscope 54700
made by Hitachi High-Technologies Corporation with a magnifying
power of 2000, and the top width (Wa) of the upper portion of the
circuit and the bottom width (Wb) of the bottom portion of the
circuit were measured. The thickness (T) of a copper foil was set
to 12 .mu.m. The etching factor (Ef) was calculated by the
following expression.
Etching factor (Ef)=(2.times.T)/(Wb-Wa)
[0366] In the case that a copper foil surface was surface treated
for providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, the surface of a surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was used for the measurement.
[0367] Measurement of Transmission Loss;
[0368] Each sample was obtained by laminating one surface of a
surface treated copper foil on a commercially available liquid
crystal polymer resin (Vecstar CTZ-50 .mu.m made by Kuraray Co.,
Ltd., a liquid crystal polymer resin as a polycondensate of
6-hydroxy-2-naphthoic acid and p-hydroxybenzoic acid).
Subsequently, a microstripline was formed on the sample by etching
such that the characteristic impedance was 50.OMEGA., the
permeation coefficient was measured with a network analyzer HP8720C
made by HP Development Company, L.P., and the transmission loss was
determined at a frequency of 20 GHz and a frequency of 40 GHz. In
order that evaluation conditions were uniformed as much as
possible, the surface treated copper foil and the liquid crystal
polymer resin were laminated and then the copper foil thickness was
set to 18 .mu.m. That is, in the case that the copper foil
thickness more than 18 .mu.m, the thickness was decreased to a
thickness of 18 .mu.m by electrolytic polishing. On the other hand,
in the case that the copper foil thickness was less than 18 .mu.m,
the thickness was increased to a thickness of 18 .mu.m by a copper
plating treatment. The transmission loss at a frequency of 20 GHz
was ranked as follow: a transmission loss at a frequency of 20 GHz
of less than 3.7 dB/10 cm was ranked as "double-circle", a
transmission loss at a frequency of 20 GHz of 3.7 dB/10 cm or more
and less than 4.1 dB/10 cm was ranked as "circle", a transmission
loss at a frequency of 20 GHz of 4.1 dB/10 cm or more and less than
5.0 dB/10 cm was ranked as "triangle", and a transmission loss at a
frequency of 20 GHz of 5.0 dB/10 cm or more was ranked as "X
mark".
[0369] In the case of a printed wiring board or a copper clad
laminate, the respective measurements can be performed with respect
to a copper circuit or a copper foil surface by melting and
removing a resin.
[0370] In the case that one surface of a copper foil was surface
treated for providing a heat-resistant layer, a rustproof layer, a
weather-resistant layer, and the like after being roughening
treated or not being roughening treated, one surface of a surface
treated copper foil after the surface treatment for providing a
heat-resistant layer, a rustproof layer, a weather-resistant layer,
and the like was used for the measurement.
[0371] Evaluation of Copper Foil Wrinkles and the Like Caused Due
to Lamination;
[0372] Each surface treated copper foil in Experimental Examples
was laminated on each of both sides of a polyimide resin having a
thickness of 25 .mu.m so that one surface thereof faced the
polyimide film, and a protective film (made of polyimide) having a
thickness of 125 .mu.m was laminated on other surface of each
surface treated copper foil, namely, five layers of protective
film/surface treated copper foil/polyimide resin/surface treated
copper foil/protective film were obtained. Lamination processing
was performed with a laminate roll from the outside of each of both
the protective films under application of heat and pressure, and
the surface treated copper foil was laminated on each of both sides
of the polyimide resin. Subsequently, the protective film on each
of both surfaces was peeled, surface treated other surface of the
copper foil was then visually observed, and the presence of
wrinkles or stripes was confirmed. A case where wrinkles and
stripes did not occur at all was ranked as "double-circle", a case
where wrinkles or stripes were observed at only one point per a
length of a copper foil of 5 m was ranked as "circle", and a case
where wrinkles or stripes were observed at two or more points per a
length of a copper foil of 5 m was ranked as "X mark".
[0373] The conditions and the evaluation of the respective tests
are described in Tables 1 to 15.
TABLE-US-00001 TABLE 1 Current Plating Roughening density time
plating bath (A/dm.sup.2) (sec) Experimental Example Cu: 15 g/L, 25
1.5 A1-17, A1-25 Co: 7 g/L Experimental Example A1-1, Ni: 10 g/L
2.0 A1-12, A1-15, A1-16 pH: 3 Experimental Example A1-10,
Temperature: 38.degree. C. 2.5 A1-13, A1-21, A1-22, A1-23
Experimental Example A1-24 3.0 Experimental Example B1-13 3.5
Experimental Example B1-6 4.0 Experimental Example A1-8, Cu: 15
g/L, 35 0.5 A1-9, A1-20, A1-27 Co: 9 g/L Experimental Example Ni: 9
g/L 0.7 A1-6, A1-7 pH: 3 Experimental Example Temperature:
38.degree. C. 0.8 A1-4, A1-5 Experimental Example A1-2, 1.4 A1-3,
A1-14 Experimental Example 2.0 B1-3, B1-4 Experimental Example
A1-30 0.2 Experimental Example Cu: 15 g/L, 45 0.5 A1-18, A1-26 Co:
9 g/L Ni: 9 g/L Experimental Example A1-19 pH: 3 1.0 Experimental
Example B1-14 Temperature: 38.degree. C. 1.5 Experimental Example
A1-11 Cu: 20 g/L, 35 1.0 Ni: 5 g/L P: 1 g/L pH: 2 Temperature:
30.degree. C. Experimental Example A1-28 Cu: 5 g/L, 35 0.8 Ni: 16
g/L Co: 16 g/L, W: 1 g/L pH: 3 Temperature: 35.degree. C.
Experimental Example A1-29 Cu: 10 g/L, 40 0.5 Ni: 10 g/L Mo: 2 g/L,
P: 1 g/L pH: 3 Temperature: 35.degree. C. Experimental Example Cu:
10 g/L, 60 1.5 B1-1, B1-2 H.sub.2SO.sub.4: 50 g/L Temperature:
25.degree. C. Experimental Example B1-9 Cu: 15 g/L, 20 2.0 Co: 8.5
g/L Experimental Example B1-10 Ni: 8.6 g/L 10 10.0 Experimental
Example B1-11 pH: 2.5 20 10.0 Experimental Example B1-12
Temperature: 38.degree. C. 20 2.0
TABLE-US-00002 TABLE 2 Metal foil (before surface treatment)
Roughness Type Thickness TD Glossiness % (ppm represents mass ppm)
Process (.mu.m) Rz (.mu.m) MD TD MD/TD Experimental Tough pitch
copper High gloss rolling, oil film equivalent 24000 12 0.66 397
243 1.63 Example A1-1 Experimental Tough pitch copper High gloss
rolling, oil film equivalent 17000 18 0.40 541 507 1.07 Example
A1-2 Experimental Tough pitch copper High gloss rolling, oil film
equivalent 17000 18 0.40 541 507 1.07 Example A1-3 Experimental
Tough pitch copper High gloss rolling, oil film equivalent 17000 18
0.40 541 507 1.07 Example A1-4 Experimental Tough pitch copper High
gloss rolling, oil film equivalent 17000 18 0.40 541 507 1.07
Example A1-5 Experimental Tough pitch copper High gloss rolling,
oil film equivalent 17000 18 0.40 541 507 1.07 Example A1-6
Experimental Tough pitch copper High gloss rolling, oil film
equivalent 17000 18 0.40 541 507 1.07 Example A1-7 Experimental
Tough pitch copper High gloss rolling, oil film equivalent 17000 18
0.40 541 507 1.07 Example A1-8 Experimental Tough pitch copper High
gloss rolling, oil film equivalent 17000 18 0.40 541 507 1.07
Example A1-9 Experimental Tough pitch copper + Ag: 180 ppm High
gloss rolling, oil film equivalent 14000 18 0.38 635 580 1.09
Example A1-10 Experimental Tough pitch copper High gloss rolling,
oil film equivalent 17000 18 0.50 549 409 1.34 Example A1-11
Experimental Oxygen-free copper + Sn: 1200 ppm Normal rolling, oil
film equivalent 30000 + 5 0.75 411 414 0.99 Example A1-12
electrolytic polishing (20 sec.) Experimental Oxygen-free copper +
Sn: 10 ppm Normal rolling, oil film equivalent 25000 12 0.60 362
351 1.03 Example A1-13 chemical polishing Experimental Oxygen-free
copper + Ag: 30 ppm High gloss rolling, oil film equivalent 12 0.25
792 771 1.03 Example A1-14 14000 + electrolytic polishing (40 sec.)
Experimental Oxygen-free copper + Ag: 100 ppm Normal rolling, oil
film equivalent 35 0.61 352 330 1.07 Example A1-15 25000 +
electrolytic polishing (20 sec.) Experimental Oxygen-free copper +
Ag: 100 ppm Normal rolling, oil film equivalent 35 0.61 352 330
1.07 Example A1-16 25000 + electrolytic polishing (20 sec.)
Experimental Electrolytic copper foil Electrolytic copper foil +
electrolytic 5 0.68 432 421 1.03 Example A1-17 polishing (40 sec.)
Experimental Electrolytic copper foil Electrolytic copper foil +
electrolytic 18 0.43 610 597 1.02 Example A1-18 polishing (60 sec.)
Experimental Oxygen-free copper + Ag: 100 ppm, High gloss rolling,
oil film equivalent 14000 12 0.36 670 611 1.10 Example A1-19 Ti: 30
ppm, Mg: 40 ppm Experimental Fe: 0.3 mass %, P: 0.1 mass % High
gloss rolling, oil film equivalent 14000 35 0.39 592 543 1.09
Example A1-20 balance Cu + unavoidable impurities Experimental Cr:
0.2 mass %, Zr: 0.1 mass % High gloss rolling, oil film equivalent
14000 12 0.35 681 612 1.11 Example A1-21 balance Cu + unavoidable
impurities Experimental Cr: 0.2 mass %, Zr: 0.1 mass % High gloss
rolling, oil film equivalent 14000 12 0.35 681 612 1.11 Example
A1-22 balance Cu + unavoidable impurities Experimental Cr: 0.2 mass
%, Zr: 0.1 mass % High gloss rolling, oil film equivalent 12 0.36
678 651 1.04 Example A1-23 balance Cu + unavoidable impurities
15000 + electrolytic polishing (5 sec.) Experimental Oxygen-free
copper + High gloss rolling, oil film equivalent 14000 18 0.38 629
571 1.10 Example A1-24 Ag: 180 ppm, Sn: 20 ppm Experimental Tough
pitch copper High gloss rolling, oil film equivalent 24000 9 0.64
401 321 1.25 Example A1-25 Experimental Tough pitch copper High
gloss rolling, oil film equivalent 13000 18 0.20 682 620 1.10
Example A1-26 Experimental Electrolytic copper foil -- 18 0.55 520
523 0.99 Example A1-27 Experimental Tough pitch copper High gloss
rolling, oil film equivalent 17000 18 0.50 549 409 1.34 Example
A1-28 Experimental Tough pitch copper High gloss rolling, oil film
equivalent 17000 18 0.50 549 409 1.34 Example A1-29 Experimental
Tough pitch copper High gloss rolling, oil film equivalent 17000 12
0.40 541 507 1.07 Example A1-30
TABLE-US-00003 TABLE 3 Metal foil (before surface treatment) Type
(ppm represents Thickness Roughness TD Glossiness % mass ppm)
Process (.mu.m) Rz (.mu.m) MD TD MD/TD Experimental Example B1-1
Tough pitch copper Normal rolling, oil film equivalent 25000 18
0.70 203 195 1.04 Experimental Example B1-2 Tough pitch copper
Normal rolling, oil film equivalent 25000 18 0.70 203 195 1.04
Experimental Example B1-3 Tough pitch copper Normal rolling, oil
film equivalent 26000 18 0.75 128 167 0.77 Experimental Example
B1-4 Tough pitch copper Normal rolling, oil film equivalent 26000
18 0.75 128 167 0.77 Experimental Example B1-5 Tough pitch copper
High gloss rolling, oil film equivalent 24000 9 0.66 397 243 1.63
Experimental Example B1-6 Tough pitch copper High gloss rolling,
oil film equivalent 17000 12 0.40 541 507 1.07 Experimental Example
B1-7 Tough pitch copper High gloss rolling, oil film equivalent
24000 18 0.80 370 321 1.15 Experimental Example B1-8 Tough pitch
copper High gloss rolling, oil film equivalent 24000 18 0.59 404
337 1.20 Experimental Example B1-9 Tough pitch copper Normal
rolling, oil film equivalent 26000 18 0.75 128 167 0.77
Experimental Example B1-10 Tough pitch copper Normal rolling, oil
film equivalent 26000 18 0.75 128 167 0.77 Experimental Example
B1-11 Tough pitch copper Normal rolling, oil film equivalent 26000
18 0.75 128 167 0.77 Experimental Example B1-12 Electrolytic copper
-- 12 0.71 131 141 0.93 foil Experimental Example B1-13 Tough pitch
copper High gloss rolling, oil film equivalent 17000 12 0.40 541
507 1.07 Experimental Example B1-14 Electrolytic copper
Electrolytic copper foil + 18 0.43 610 597 1.02 foil electrolytic
polishing (60 sec.) Experimental Example B1-15 Tough pitch copper
High gloss rolling, oil film equivalent 24000 9 0.66 397 243
1.63
TABLE-US-00004 TABLE 4 Difference between top Composition of
average and roughening bottom treatment average in Surface treated
metal foil bath, plating Resin brightness Glossiness time thickness
curve Sv = 0.1.DELTA.B/ Roughness MD TD MD/TD (Table 1) (.mu.m)
.DELTA.B (t1 - t2) TD Rz (.mu.m) (%) (%) (--) Experimental Example
A1-1 2.0 sec. 50 43 3.5 0.66 91 70 1.30 Experimental Example A1-2
1.4 sec. 25 68 6.8 0.46 94 75 1.25 Experimental Example A1-3 1.4
sec. 50 47 5.9 0.46 94 75 1.25 Experimental Example A1-4 0.8 sec.
25 64 6.4 0.45 143 120 1.19 Experimental Example A1-5 0.8 sec. 50
52 5.2 0.45 143 120 1.19 Experimental Example A1-6 0.7 sec. 25 61
6.1 0.44 222 196 1.13 Experimental Example A1-7 0.7 sec. 50 55 5.6
0.44 222 196 1.13 Experimental Example A1-8 0.5 sec. 25 68 5.2 0.42
298 356 0.84 Experimental Example A1-9 0.5 sec. 50 49 6.1 0.42 298
356 0.84 Experimental Example A1-10 2.5 sec. 50 54 3.8 0.40 90 80
1.13 Experimental Example A1-11 1.0 sec. 50 43 3.6 0.56 122 87 1.40
Experimental Example A1-12 2.0 sec. 25 55 5.0 0.80 134 145 0.92
Experimental Example A1-13 2.5 sec. 25 53 4.4 0.62 101 98 1.03
Experimental Example A1-14 1.4 sec. 50 73 5.8 0.30 349 341 1.02
Experimental Example A1-15 2.0 sec. 25 62 6.3 0.63 209 191 1.09
Experimental Example A1-16 2.0 sec. 50 55 5.7 0.63 209 191 1.09
Experimental Example A1-17 1.5 sec. 50 38 3.7 0.72 115 100 1.15
Experimental Example A1-18 0.5 sec. 50 56 4.0 0.49 142 131 1.08
Experimental Example A1-19 1.0 sec. 50 50 5.4 0.37 112 98 1.14
Experimental Example A1-20 0.5 sec. 25 66 6.5 0.40 295 392 0.75
Experimental Example A1-21 2.5 sec. 25 61 6.2 0.41 181 123 1.47
Experimental Example A1-22 2.5 sec. 50 56 5.1 0.41 181 123 1.47
Experimental Example A1-23 2.5 sec. 25 67 6.4 0.42 182 131 1.39
Experimental Example A1-24 3.0 sec. 50 42 4.1 0.42 80 71 1.13
Experimental Example A1-25 1.5 sec. 50 51 5.0 0.65 120 101 1.19
Experimental Example A1-26 0.5 sec. 50 69 6.7 0.32 122 102.0 1.20
Experimental Example A1-27 0.5 sec. 25 68 6.6 0.60 115 114.0 1.01
Experimental Example A1-28 0.8 sec. 50 55 5.4 0.54 109 99.0 1.10
Experimental Example A1-29 0.5 sec. 50 57 5.6 0.53 118 98.0 1.20
Experimental Example A1-30 0.2 sec. 50 58 3.7 0.42 360 301 1.20
Surface treated metal foil Solder Surface Surface Peel heat Etching
area (A) area ratio strength resistance factor Transmission
.mu.m.sup.2 A/B Visibility kg/cm evaluation Yield Ef loss
Experimental Example A1-1 20230.4 2.03 .largecircle. 1.10
.circleincircle. .circleincircle. 2.0 .largecircle. Experimental
Example A1-2 20218.4 2.03 .circleincircle. 1.30 .circleincircle.
.circleincircle. 2.3 .largecircle. Experimental Example A1-3
20218.4 2.03 .circleincircle. 1.40 .circleincircle.
.circleincircle. 2.3 .largecircle. Experimental Example A1-4
20086.6 2.01 .circleincircle. 1.20 .circleincircle.
.circleincircle. 2.5 .circleincircle. Experimental Example A1-5
20086.6 2.01 .circleincircle. 1.30 .circleincircle.
.circleincircle. 2.5 .circleincircle. Experimental Example A1-6
20076.2 2.01 .circleincircle. 1.00 .circleincircle.
.circleincircle. 2.6 .circleincircle. Experimental Example A1-7
20076.2 2.01 .circleincircle. 1.20 .circleincircle.
.circleincircle. 2.6 .circleincircle. Experimental Example A1-8
20185.0 2.02 .circleincircle. 1.15 .circleincircle.
.circleincircle. 2.4 .circleincircle. Experimental Example A1-9
20185.0 2.02 .circleincircle. 1.30 .circleincircle.
.circleincircle. 2.4 .circleincircle. Experimental Example A1-10
20364.3 2.04 .circleincircle. 1.40 .circleincircle.
.circleincircle. 2.6 .circleincircle. Experimental Example A1-11
20190.4 2.02 .circleincircle. 1.80 .circleincircle.
.circleincircle. 2.6 .circleincircle. Experimental Example A1-12
23988.6 2.40 .circleincircle. 1.10 .circleincircle.
.circleincircle. 2.0 .largecircle. Experimental Example A1-13
20090.4 2.01 .circleincircle. 1.10 .largecircle. .circleincircle.
2.2 .circleincircle. Experimental Example A1-14 18991.0 1.90
.circleincircle. 1.00 .largecircle. .circleincircle. 2.8
.circleincircle. Experimental Example A1-15 19790.6 1.98
.circleincircle. 1.30 .largecircle. .circleincircle. 2.6
.largecircle. Experimental Example A1-16 19790.6 1.98
.circleincircle. 1.40 .largecircle. .circleincircle. 2.6
.largecircle. Experimental Example A1-17 22289.4 2.23 .largecircle.
1.60 .largecircle. .largecircle. 2.0 .largecircle. Experimental
Example A1-18 23089.0 2.31 .circleincircle. 1.50 .largecircle.
.circleincircle. 2.4 .circleincircle. Experimental Example A1-19
19990.5 2.00 .circleincircle. 1.30 .circleincircle.
.circleincircle. 2.4 .circleincircle. Experimental Example A1-20
19890.5 1.99 .circleincircle. 1.50 .largecircle. .circleincircle.
2.1 .circleincircle. Experimental Example A1-21 21189.9 2.12
.circleincircle. 1.00 .largecircle. .circleincircle. 2.5
.largecircle. Experimental Example A1-22 21189.9 2.12
.circleincircle. 1.20 .largecircle. .circleincircle. 2.5
.largecircle. Experimental Example A1-23 21689.7 2.17
.circleincircle. 1.15 .circleincircle. .circleincircle. 2.5
.largecircle. Experimental Example A1-24 20364.3 2.31
.circleincircle. 1.30 .circleincircle. .largecircle. 2.0
.largecircle. Experimental Example A1-25 20154.3 2.02
.circleincircle. 0.85 .largecircle. .circleincircle. 2.1
.largecircle. Experimental Example A1-26 20098.6 2.01
.circleincircle. 1.40 .circleincircle. .circleincircle. 2.8
.circleincircle. Experimental Example A1-27 20204.6 2.02
.circleincircle. 1.70 .circleincircle. .circleincircle. 2.4
.circleincircle. Experimental Example A1-28 20350.1 2.04
.circleincircle. 1.40 .largecircle. .circleincircle. 2.5
.circleincircle. Experimental Example A1-29 20289.0 2.03
.circleincircle. 1.40 .largecircle. .circleincircle. 2.3
.circleincircle. Experimental Example A1-30 20087.2 2.01
.circleincircle. 0.67 .largecircle. .circleincircle. 3.0
.circleincircle.
TABLE-US-00005 TABLE 5 Difference between top average and
Composition of bottom roughening average in Surface treated metal
foil treatment bath, Resin brightness Glossiness plating time
thickness curve Sv = 0.1.DELTA.B/ Roughness MD TD MD/TD (Table 1)
(.mu.m) .DELTA.B (t1 - t2) TD Rz (.mu.m) (%) (%) (--) Experimental
Example B1-1 1.5 sec. 25 25 1.4 1.10 1.6 1.8 0.89 Experimental
Example B1-2 1.5 sec. 50 20 1.3 1.10 1.6 1.8 0.89 Experimental
Example B1-3 2.0 sec. 25 37 2.8 0.78 0.7 0.8 0.88 Experimental
Example B1-4 2.0 sec. 50 27 2.3 0.78 0.7 0.8 0.88 Experimental
Example B1-5 (No roughening) 50 40 3.6 0.66 406 249 1.63
Experimental Example B1-6 4.0 sec. 50 25 2.1 0.48 19 12 1.58
Experimental Example B1-7 (No roughening) 50 60 3.7 0.80 375 326
1.15 Experimental Example B1-8 (No roughening) 50 61 3.7 0.59 409
342 1.20 Experimental Example B1-9 2.0 sec. 50 24 1.9 0.79 3.2 4.2
0.76 Experimental Example B1-10 10.0 sec. 25 33 3.3 0.98 1.1 1.2
0.92 Experimental Example B1-11 10.0 sec. 50 21 1.9 1.34 0.5 0.4
1.25 Experimental Example B1-12 2.0 sec. 25 34 1.7 1.12 0.6 0.7
0.86 Experimental Example B1-13 3.5 sec. 50 20 1.2 0.47 75 67 1.12
Experimental Example B1-14 1.5 sec. 25 39 3.4 0.49 142 131 1.08
Experimental Example B1-15 (No roughening) 50 38 3.4 0.66 381 242
1.57 Surface treated metal foil Solder Surface Surface Peel heat
Etching area (A) area ratio strength resistance factor Transmission
.mu.m.sup.2 A/B Visibility kg/cm evaluation Yield Ef loss
Experimental Example B1-1 23790.2 2.38 X 2.20 X X 1.1 .DELTA.
Experimental Example B1-2 23790.2 2.38 X 2.30 X X 1.1 .DELTA.
Experimental Example B1-3 22404.0 2.24 X 1.80 X .DELTA. 1.8 .DELTA.
Experimental Example B1-4 22404.0 2.24 X 1.95 X .DELTA. 1.8 .DELTA.
Experimental Example B1-5 20092.2 2.01 .circleincircle. 0.68 X
.circleincircle. 2.5 .circleincircle. Experimental Example B1-6
20698.5 2.07 X 1.40 X .DELTA. 1.9 .DELTA. Experimental Example B1-7
15428.2 1.54 .circleincircle. 0.50 X .circleincircle. 2.6
.largecircle. Experimental Example B1-8 15334.1 1.53
.circleincircle. 0.50 X .circleincircle. 2.1 .circleincircle.
Experimental Example B1-9 20398.5 2.04 X 1.85 X .DELTA. 1.6 .DELTA.
Experimental Example B1-10 20700.0 2.07 X 1.74 X .DELTA. 1.7 X
Experimental Example B1-11 24800.0 2.48 X 1.93 X X 1.8 X
Experimental Example B1-12 24498.2 2.45 X 2.23 X X 1.3 X
Experimental Example B1-13 20698.51 2.01 X 1.10 X X 1.8
.largecircle. Experimental Example B1-14 24998.2 2.50 X 1.80 X
.DELTA. 1.9 .largecircle. Experimental Example B1-15 20904.5 2.03 X
0.68 X X 2.3 .circleincircle.
TABLE-US-00006 TABLE 6 Metal foil (before surface treatment) Rough-
ness Glossiness Thick- TD TD Type Process ness Rz (.mu.m) (%)
Example A2-1 Tough pitch copper High gloss rolling, oil film 5 um
0.40 500 equivalent 17,000 Example A2-2 Tough pitch copper + High
gloss rolling, oil film 70 um 0.38 550 Ag180 ppm equivalent 17,000
Example A2-3 Tough pitch copper High gloss rolling, oil film 18 um
0.50 410 equivalent 25,000 Example A2-4 Electrolyte copper foil
Electrolyte copper foil 18 um 0.50 500 Example A2-5 Tough pitch
copper + Zn200 ppm + Normal rolling, oil film 18 um 0.55 310 Ni200
ppm + Cr50 ppm equivalent 26,000 Example A2-6 Oxygen free copper +
Ag10 ppm High gloss rolling, oil film 18 um 0.35 650 equivalent
14,000 Example A2-7 Oxygen free copper + High gloss rolling, oil
film 18 um 0.50 410 Sn2500 ppm equivalent 25,000 Example B2-1 Tough
pitch copper Normal rolling, oil film 18 um 0.70 193 equivalent
26,000 Example B2-2 Tough pitch copper High gloss rolling, oil film
18 um 0.40 500 equivalent 17,000
TABLE-US-00007 TABLE 7 Surface treatment Resin Rough- Surface
thick- Rough- Current Plating ness Area Peel Etching Trans- ness
ening Plating density time TD ratio strength Visi- factor mission
(.mu.m) treatment bath (A/dm.sup.2) (sec) Rz (.mu.m) A/B Rsk (N/mm)
Yield Sv bility EF loss Example A2-1 50 Present *1 35 1.2 0.50 1.55
-0.35 1.50 3.5 2.0 .circleincircle. Example A2-2 50 Present 35 1.0
0.42 1.43 -0.30 1.40 .circleincircle. 5.2 .circleincircle. 2.4
.circleincircle. Example A2-3 50 Present *2 30 1.0 0.56 1.23 0.24
1.60 .circleincircle. 3.7 .circleincircle. 2.0 .circleincircle.
Example A2-4 50 Present 35 0.8 0.65 1.10 0.13 1.70 3.5 2.1
.circleincircle. Example A2-5 50 Absent *3 6 1.0 0.55 1.20 -0.10
1.10 .circleincircle. 6.0 .circleincircle. 2.4 .circleincircle.
Example A2-6 50 Absent 0.38 1.03 0.39 1.00 .circleincircle. 4.3
.circleincircle. 2.2 .circleincircle. Example A2-7 50 Absent 0.51
1.01 0.53 1.55 3.5 2.0 .circleincircle. Example B2-1 50 Present *1
35 2.0 0.80 1.80 -0.39 1.70 .times. 2.8 .times. 1.8 .DELTA. Example
B2-2 50 Present *4 0.80 1.50 0.64 1.80 .times. 1.8 .times. 1.5 *1
Cu 15 g/L, Co 8.5 g/L, Ni 8.6 g/L, pH 2.5, 38.degree. C. *2 Cu 10
g/L, Ni 20 g/L, P1 g/L, pH 2.5, 40.degree. C. *3 Ni 20 g/L, pH 2.5,
40.degree. C. *4 (Cu 15 g/L, H.sub.2SO.sub.4 50 g/L, 25.degree. C.,
50 A/dm.sup.2, 1.5 sec) + (Cu 20 g/L, H.sub.2SO.sub.4 100 g/L,
50.degree. C., 2A/dm.sup.2, 15 sec)
TABLE-US-00008 TABLE 8 Metal foil (before surface treatment)
Roughness Glossiness TD TD Type Process Thickness Rz (.mu.m) (%)
Experimental Example B3-1 Tough pitch copper High gloss rolling,
oil film equivalent 8,500 18 um 0.12 740 Experimental Example A3-1
Tough pitch copper High gloss rolling, oil film equivalent 9,500 18
um 0.20 710 Experimental Example A3-2 Electrolytic Copper 100 g/L,
Sulfuric acid 100 g/L, Chlorine 50 ppm, 18 um 0.23 660 copper foil
Leveling agent 1:10-30 ppm, Leveling agent 2:10-30 ppm, Electrolyte
temperature 50-60.degree. C., Current density 70-100 A/dm.sup.2,
Electrolysis time 1 min, Linear velocity of electrolyte 4 m/sec
Experimental Example A3-3 Tough pitch copper High gloss rolling,
oil film equivalent 12,000 18 um 0.26 640 Experimental Example A3-4
Tough pitch copper High gloss rolling, oil film equivalent 14,000
18 um 0.40 590 Experimental Example A3-5 Tough pitch copper High
gloss rolling, oil film equivalent 17,000 18 um 0.42 500
Experimental Example A3-6 Tough pitch copper High gloss rolling,
oil film equivalent 17,000 18 um 0.42 500 Experimental Example A3-7
Tough pitch copper High gloss rolling, oil film equivalent 17,000
18 um 0.42 500 Experimental Example A3-8 Tough pitch copper High
gloss rolling, oil film equivalent 17,000 18 um 0.42 500
Experimental Example A3-9 Tough pitch copper High gloss rolling,
oil film equivalent 17,000 18 um 0.42 500 Experimental Example B3-2
Tough pitch copper High gloss rolling, oil film equivalent 17,000
18 um 0.42 500 Experimental Example B3-3 Tough pitch copper High
gloss rolling, oil film equivalent 17,000 18 um 0.42 500
Experimental Example B3-4 Tough pitch copper High gloss rolling,
oil film equivalent 18,000 18 um 0.58 380 Experimental Example B3-5
Tough pitch copper High gloss rolling, oil film equivalent 19,000
18 um 0.61 350
TABLE-US-00009 TABLE 9 Surface treatment Resin Current Plating
Surface thickness Roughening density time Roughness area ratio
(.mu.m) treatment Plating bath (A/dm.sup.2) (sec) TD Rz (.mu.m) D/C
Experimental Example B3-1 50 Absent Ni 20 g/L 6 1.0 0.12 1.0
Experimental Example A3-1 50 Absent pH 2.5 0.20 1.0 Experimental
Example A3-2 50 Absent 40.degree. C. 0.23 1.0 Experimental Example
A3-3 50 Absent 0.26 1.0 Experimental Example A3-4 50 Absent 0.40
1.0 Experimental Example A3-5 50 Present Cu 15 g/L 30 1.0 0.43 1.2
Experimental Example A3-6 50 Present Co 8.5 g/L 35 1.0 0.46 1.4
Experimental Example A3-7 50 Present Ni 8.6 g/L 35 1.3 0.55 1.5
Experimental Example A3-8 50 Present pH 2.5 35 1.7 0.62 1.6
Experimental Example A3-9 50 Present 38.degree. C. 40 1.7 0.64 1.7
Experimental Example B3-2 50 Present 40 2.0 0.70 1.8 Experimental
Example B3-3 50 Present 50 1.5 0.74 1.9 Experimental Example B3-4
50 Absent Ni 0.3 g/L 7 5.0 0.58 1.6 Experimental Example B3-5 50
Absent Zn 2.5 g/L 5 4.5 0.61 1.7 Pyrophosphoric acid 40.degree. C.
Peel Solder heat Rq strength resistance Etching Transmission
(.mu.m) (N/mm) evaluation Yield Sv Visibility factor Ef loss
Experimental Example B3-1 0.10 0.65 X .circleincircle. 7.0
.circleincircle. 3.0 .circleincircle. Experimental Example A3-1
0.14 0.70 .largecircle. .circleincircle. 7.0 .circleincircle. 3.0
.circleincircle. Experimental Example A3-2 0.20 0.72 .largecircle.
.circleincircle. 6.5 .circleincircle. 2.8 .largecircle.
Experimental Example A3-3 0.25 0.72 .circleincircle.
.circleincircle. 6.5 .circleincircle. 2.7 .circleincircle.
Experimental Example A3-4 0.32 0.76 .circleincircle.
.circleincircle. 6.0 .circleincircle. 2.6 .circleincircle.
Experimental Example A3-5 0.40 0.80 .circleincircle.
.circleincircle. 6.0 .circleincircle. 2.5 .circleincircle.
Experimental Example A3-6 0.51 0.80 .circleincircle.
.circleincircle. 6.0 .circleincircle. 2.5 .circleincircle.
Experimental Example A3-7 0.56 0.82 .circleincircle.
.circleincircle. 5.0 .circleincircle. 2.3 .largecircle.
Experimental Example A3-8 0.60 0.82 .circleincircle.
.circleincircle. 3.9 .circleincircle. 2.0 .largecircle.
Experimental Example A3-9 0.63 0.82 .circleincircle. .largecircle.
3.5 .largecircle. 2.0 .largecircle. Experimental Example B3-2 0.67
0.85 .circleincircle. .DELTA. 3.0 X 1.8 .DELTA. Experimental
Example B3-3 0.77 0.90 .circleincircle. X 2.5 X 1.6 .DELTA.
Experimental Example B3-4 0.65 0.80 .circleincircle. X 3.3 X 1.9
.circleincircle. Experimental Example B3-5 0.66 0.83
.circleincircle. X 3.1 X 1.9 .circleincircle.
TABLE-US-00010 TABLE 10 Metal foil (before surface treatment)
Roughness Glossiness TD TD Type Process Thickness Rz (.mu.m) (%)
Experimental Example B4-1 Tough pitch copper High gloss rolling,
oil film equivalent 8,500 18 um 0.12 740 Experimental Example A4-1
Tough pitch copper High gloss rolling, oil film equivalent 9,500 18
um 0.20 710 Experimental Example A4-2 Electrolytic Copper 100 g/L,
Sulfuric acid 100 g/L, Chlorine 50 ppm, 18 um 0.23 660 copper foil
Leveling agent 1:10-30 ppm, Leveling agent 2:10-30 ppm, Electrolyte
temperature 50-60.degree. C., Current density 70-100A/dm.sup.2,
Electrolysis time 1 min, Linear velocity of electrolyte 4 m/sec
Experimental Example A4-3 Tough pitch copper High gloss rolling,
oil film equivalent 12,000 18 um 0.26 640 Experimental Example A4-4
Tough pitch copper High gloss rolling, oil film equivalent 14,000
18 um 0.40 590 Experimental Example A4-5 Tough pitch copper High
gloss rolling, oil film equivalent 17,000 18 um 0.42 500
Experimental Example A4-6 Tough pitch copper High gloss rolling,
oil film equivalent 17,000 18 um 0.42 500 Experimental Example A4-7
Tough pitch copper High gloss rolling, oil film equivalent 17,000
18 um 0.42 500 Experimental Example A4-8 Tough pitch copper High
gloss rolling, oil film equivalent 17,000 18 um 0.55 400
Experimental Example B4-2 Tough pitch copper High gloss rolling,
oil film equivalent 20,000 18 um 0.68 200 Experimental Example B4-3
Tough pitch copper High gloss rolling, oil film equivalent 20,000
18 um 0.68 200 Experimental Example B4-4 Tough pitch copper High
gloss rolling, oil film equivalent 18,000 18 um 0.58 380
Experimental Example B4-5 Tough pitch copper High gloss rolling,
oil film equivalent 19,000 18 um 0.61 350
TABLE-US-00011 TABLE 11 Surface treatment Surface Resin Current
Plating Roughness area thickness Roughening density time TD Rz
ratio Measurement (.mu.m) treatment Plating bath (A/dm.sup.2) (sec)
(.mu.m) D/C area G (.mu.m.sup.2) Experimental 50 Absent Ni 20 g/L 6
1.0 0.12 1.0 417,953 Example B4-1 pH 2.5 Experimental 50 Absent
40.degree. C. 0.20 1.0 417,953 Example A4-1 Experimental 50 Absent
0.23 1.0 417,953 Example A4-2 Experimental 50 Absent 0.26 1.0
417,953 Example A4-3 Experimental 50 Absent 0.40 1.0 417,952
Example A4-4 Experimental 50 Present Cu 15 g/L 35 1.0 0.46 1.4
417,953 Example A4-5 Co 8.5 g/L Experimental 50 Present Ni 8.6 g/L
35 1.3 0.55 1.5 417,953 Example A4-6 pH 2.5 Experimental 50 Present
38.degree. C. 35 1.7 0.62 1.6 417,953 Example A4-7 Experimental 50
Present 40 1.7 0.64 1.7 417,953 Example A4-8 Experimental 50
Present 50 1.5 0.74 1.9 417,953 Example B4-2 Experimental 50
Present 50 2.0 0.80 2.0 417,953 Example B4-3 Experimental 50 Absent
Ni 0.3 g/L 7 5.0 0.58 1.6 417,953 Example B4-4 Zn 2.5 g/L
Experimental 50 Absent Pyrophosphoric 5 4.5 0.61 1.7 417,953
Example B4-5 acid 40.degree. C. Solder Measurement Peel heat volume
E strength resistance Etching Transmission (.mu.m.sup.3) E/G (N/mm)
evaluation Yield Sv Visibility factor Ef loss Experimental 758,685
1.82 0.65 X .circleincircle. 7.0 .circleincircle. 3.0
.circleincircle. Example B4-1 Experimental 882,196 2.11 0.70
.largecircle. .circleincircle. 7.0 .circleincircle. 3.0
.circleincircle. Example A4-1 Experimental 1,020,383 2.44 0.72
.largecircle. .circleincircle. 6.5 .circleincircle. 2.8
.largecircle. Example A4-2 Experimental 1,232,196 2.95 0.72
.largecircle. .circleincircle. 6.5 .circleincircle. 2.7
.circleincircle. Example A4-3 Experimental 2,844,915 6.81 0.76
.circleincircle. .circleincircle. 6.0 .circleincircle. 2.6
.circleincircle. Example A4-4 Experimental 4,407,151 10.54 0.80
.circleincircle. .circleincircle. 6.0 .circleincircle. 2.5
.circleincircle. Example A4-5 Experimental 5,560,760 13.30 0.82
.circleincircle. .circleincircle. 5.0 .circleincircle. 2.3
.largecircle. Example A4-6 Experimental 8,954,423 21.42 0.82
.circleincircle. .circleincircle. 3.9 .circleincircle. 2.0
.largecircle. Example A4-7 Experimental 9,994,423 23.91 0.82
.circleincircle. .largecircle. 3.5 .largecircle. 2.0 .largecircle.
Example A4-8 Experimental 10,665,609 25.52 0.90 .circleincircle. X
2.5 X 1.6 .DELTA. Example B4-2 Experimental 13,665,609 32.70 0.95
.circleincircle. X 1.5 X 1.2 .DELTA. Example B4-3 Experimental
9,800,998 23.45 0.80 .circleincircle. X 3.3 X 1.9 .circleincircle.
Example B4-4 Experimental 11,418,476 27.32 0.83 .circleincircle. X
3.1 X 1.9 .circleincircle. Example B4-5
TABLE-US-00012 TABLE 12 Surface treatment of other surface Wrinkles
or Current Rz of other Ra of other Rq of other stripes on density
Plating time surface surface surface other Plating bath
(A/dm.sup.2) (sec) (.mu.m) (.mu.m) (.mu.m) surface A1-1 Cu: 15 g/L,
15 15 0.81 0.1 0.14 .circleincircle. A1-2 Co: 9 g/L, 0.61 0.06 0.1
.circleincircle. A1-3 Ni: 9 g/L 0.61 0.06 0.1 .circleincircle. A1-4
pH: 3 20 3 0.75 0.07 0.11 .circleincircle. A1-5 Temperature:
38.degree. C. 0.75 0.07 0.11 .circleincircle. A1-6 0.75 0.07 0.11
.circleincircle. A1-7 25 2 0.62 0.06 0.1 .circleincircle. A1-8 0.62
0.06 0.1 .circleincircle. A1-9 0.62 0.06 0.1 .circleincircle. A1-10
30 1 0.42 0.05 0.09 .largecircle. A1-11 0.65 0.06 0.1
.circleincircle. A1-12 0.85 0.07 0.15 .circleincircle. A1-13 35 1
0.68 0.06 0.11 .circleincircle. A1-14 0.35 0.05 0.08 .largecircle.
A1-15 0.59 0.06 0.09 .circleincircle. A1-16 40 3 1.06 0.09 0.15
.circleincircle. A1-17 1.15 0.1 0.16 .circleincircle. A1-18 1.25
0.11 0.18 .circleincircle. A1-19 Cu: 10 g/L, 60 2 1.4 0.16 0.23
.circleincircle. A1-20 H2SO4: 50 g/L, 1.45 0.17 0.24
.circleincircle. A1-21 Temperature: 25.degree. C. 1.55 0.2 0.27
.circleincircle. A1-22 Cu: 20 g/L, 40 15 0.67 0.06 0.1
.circleincircle. A1-23 H2SO4: 100 g/L, 0.68 0.07 0.1
.circleincircle. A1-24 Temperature: 50.degree. C. 0.7 0.07 0.12
.circleincircle. A1-25 Cu: 20 g/L, 40 0.5 0.67 0.07 0.1
.circleincircle. A1-26 Ni: 5 g/L, 1 0.36 0.05 0.08 .largecircle.
A1-27 P: 1 g/L, 2 0.52 0.06 0.09 .circleincircle. pH: 2,
Temperature: 30.degree. C. A1-28 Ni: 30 g/L, 1.5 10 0.61 0.06 0.1
.circleincircle. A1-29 Zn: 10 g/L, 0.65 0.06 0.1 .circleincircle.
A1-30 pH: 5 0.68 0.06 0.11 .circleincircle. Temperature: 40.degree.
C. B1-5 Cu: 15 g/L, 30 0.8 0.73 0.07 0.11 .circleincircle. B1-7 Co:
9 g/L, 0.84 0.11 0.14 .circleincircle. B1-8 Ni: 9 g/L 0.66 0.06
0.09 .circleincircle. pH: 3 Temperature: 38.degree. C. B1-1 No
treatment -- -- 0.6 0.06 0.1 X B1-2 0.61 0.06 0.1 X B1-3 0.65 0.06
0.1 X B1-4 0.65 0.06 0.1 X B1-6 0.34 0.04 0.07 X B1-9 0.65 0.06 0.1
X B1-10 0.65 0.06 0.1 X B1-11 -- -- 0.65 0.06 0.1 X B1-12 0.6 0.06
0.1 X B1-13 0.34 0.04 0.06 X B1-14 0.38 0.04 0.07 X B1-15 0.59 0.05
0.09 X B1-16 No treatment -- -- 0.31 0.038 0.053 X B1-17 No
treatment -- -- 0.27 0.033 0.045 X B1-18 No treatment -- -- 0.34
0.04 0.07 X
TABLE-US-00013 TABLE 13 Surface treatment of other surface Wrinkles
or Current Rz of other Ra of other Rq of other stripes on density
Plating surface surface surface other Plating bath (A/dm.sup.2)
time (sec) (.mu.m) (.mu.m) (.mu.m) surface A2-1 Cu: 15 g/L, 25 1.5
0.59 0.06 0.1 .circleincircle. A2-2 Co: 7 g/L, 0.4 0.05 0.09
.largecircle. A2-3 Ni: 7 g/L 35 1 0.65 0.06 0.1 .circleincircle.
A2-4 pH: 3 0.63 0.06 0.1 .circleincircle. A2-5 Temperature:
38.degree. C. 40 0.7 0.71 0.07 0.12 .circleincircle. A2-6 Cu: 20
g/L, 35 15 0.35 0.05 0.08 .circleincircle. A2-7 H2SO4: 100 g/L,
0.59 0.06 0.09 .circleincircle. Temperature: 50.degree. C. B2-1 No
surface treatment -- -- 0.75 0.07 0.08 X B2-2 0.5 0.06 0.08 X
TABLE-US-00014 TABLE 14 Surface treatment of other surface Wrinkles
or Current Rz of other Ra of other Rq of other stripes on density
Plating surface surface surface other Plating bath (A/dm.sup.2)
time (sec) (.mu.m) (.mu.m) (.mu.m) surface A3-1 Cu: 15 g/L, 25 1
0.35 0.05 0.08 .largecircle. A3-2 Co: 7 g/L, 0.36 0.05 0.08
.largecircle. A3-3 Ni: 7 g/L, 30 1 0.37 0.06 0.1 .circleincircle.
A3-4 pH: 3 0.39 0.07 0.12 .circleincircle. A3-5 Temperature:
38.degree. C. 35 2 1.21 0.18 0.25 .circleincircle. A3-6 1.33 0.23
0.61 .circleincircle. A3-7 40 2 1.64 0.28 0.67 .circleincircle.
B3-1 40 1 0.35 0.05 0.08 .largecircle. A3-8 Cu: 20 g/L, H2SO4: 100
g/L, 15 15 0.44 0.06 0.12 .circleincircle. A3-9 Temperature
50.degree. C. 20 0.56 0.07 0.15 .circleincircle. (electrolytic
polishing) B3-2 No surface treatment -- -- 0.34 0.04 0.07 X B3-3
0.34 0.04 0.07 X B3-4 0.53 0.05 0.08 X B3-5 0.56 0.06 0.09 X
TABLE-US-00015 TABLE 15 Surface treatment of other surface Wrinkles
or Current Rz of other Ra of other Rq of other stripes on density
Plating surface surface surface other Plating bath (A/dm.sup.2)
time (sec) (.mu.m) (.mu.m) (.mu.m) surface A4-1 Cu: 20 g/L, 25 0.8
0.35 0.05 0.08 .largecircle. A4-2 Ni: 5 g/L, 1.5 0.38 0.07 0.11
.circleincircle. A4-3 P: 1 g/L, 2.5 0.56 0.1 0.19 .circleincircle.
pH; 2, Temperature: 30.degree. C. A4-4 Cu: 10 g/L, 60 0.8 0.61 0.12
0.21 .circleincircle. A4-5 H2SO4: 50 g/L, 4 2.43 0.32 0.76
.circleincircle. A4-6 Temperature: 25.degree. C. 7 3.34 0.54 0.93
.circleincircle. A4-7 Ni: 30 g/L, 1 15 0.54 0.09 0.12
.circleincircle. A4-8 Zn: 10 g/L, 1.5 10 0.57 0.1 0.13
.circleincircle. B4-1 pH: 5 2 8 0.36 0.05 0.09 .largecircle.
Temperature: 40.degree. C. B4-2 No surface treatment -- -- 0.58
0.07 0.09 X B4-3 0.58 0.07 0.09 X B4-4 0.55 0.06 0.08 X B4-5 0.54
0.06 0.08 X
[0374] In Experimental Examples where the Sv was in the range of
the present invention, good visibility and good yield were
achieved.
[0375] In Experimental Examples where other surface was surface
treated, the occurrence of wrinkles and stripes on the other
surface of a copper foil was well suppressed by double-sided
lamination.
[0376] The SEM observation photographs of the copper foil surfaces
in Experimental Example B3-1, Experimental Example A3-1,
Experimental Example A3-2, Experimental Example A3-3, Experimental
Example A3-4, Experimental Example A3-5, Experimental Example A3-6,
Experimental Example A3-7, Experimental Example A3-8, Experimental
Example A3-9, Experimental Example B3-2, and Experimental Example
B3-3 for the evaluation of Rz are shown in FIGS. 4(a), 4(b), 4(c),
4 (d), 4(e), 4(f), 4(g), 4(h), 4(i), 4(j), 4(k), and 4(l),
respectively.
[0377] In Examples, the width of the mark were changed from 0.3 mm
to 0.16 mm (a mark arranged thirdly closer to the description 0.5
having an area of 0.5 mm.sup.2 in the sheet of dirt (mark indicated
by arrow in FIG. 7)) for the same measurement of .DELTA.B and t1,
t2, Sv. As a result, the same values as for the mark having a width
of 0.3 mm were obtained in any of the .DELTA.B and t1, t2, Sv.
[0378] Furthermore, in Examples, the "top average Bt of brightness
curve" representing the average of brightness measured at 5 spots
at intervals of 30 .mu.m from a position 50 .mu.m away from the end
position of both sides of the mark (total 10 spots on both sides)
was changed to the average of brightness measured at 5 spots at
intervals of 30 .mu.m from a position 100 .mu.m away, from a
position 300 .mu.m away, and from a position 500 .mu.m away, from
the end position of both sides of the mark (total 10 spots on both
sides), respectively for the same measurement of .DELTA.B and t1,
t2, Sv. As a result, the same values as for the "top average Bt of
brightness curve" representing the average of brightness measured
at 5 spots at intervals of 30 .mu.m from a position 50 .mu.m away
from the end position of both sides of the mark (total 10 spots on
both sides) were obtained in any of the .DELTA.B and t1, t2,
Sv.
[0379] The same copper foil as in Experimental Examples above was
used and both surfaces thereof were surface treated under the same
conditions as those in the surface treatment of one surface so as
to produce a surface treated copper foil. The surface treated
copper foil was used for the evaluations, and the evaluation
results of both surfaces were the same as those of one surface in
each Experimental Example. In the case that a copper foil was
subjected to electrolytic polishing or chemical polishing, both
surfaces were subjected to electrolytic polishing or chemical
polishing and then surface treated. In Experimental Example A1-27,
Experimental Example B1-12, and Experimental Example A2-4, a glossy
surface (a surface in contact with a drum in manufacturing of an
electrolyte copper foil) of a copper foil was subjected to
electrolytic polishing and/or chemical polishing so as to have the
same TD roughness Rz and glossiness as those of a deposition
surface, and then was subjected to a predetermined surface
treatment or formation of an interlayer and the like.
[0380] In the case that both surfaces of a copper foil are surface
treated, for example, roughening treated, both surfaces may be
simultaneously surface treated or one surface and other surface may
be separately surface treated. In the case that both surfaces are
simultaneously surface treated, both surfaces of a copper foil may
be surface treated with a surface treatment device (plating device)
provided with an anode. In the present Experimental Examples, both
surfaces were simultaneously surface treated.
[0381] All roughening treated copper foil surfaces in respective
Experimental Examples had a TD ten-spot average roughness Rz
measured with a laser microscope using laser light having a
wavelength of 405 nm, of 0.35 .mu.m or more. In addition, all
roughening treated copper foil surfaces in respective Experimental
Examples had a TD arithmetic average roughness Ra measured with a
laser microscope using laser light having a wavelength of 405 nm,
of 0.05 .mu.m or more. Moreover, all roughening treated copper foil
surfaces in respective Experimental Examples had a TD root mean
square height Rq measured with a laser microscope using laser light
having a wavelength of 405 nm, of 0.08 .mu.m or more.
* * * * *